Metal coordinating and film-forming materials

ABSTRACT

Film-forming materials include nonionic metal coordinating structures. Nonionic metal coordinating structures can coordinate metals, such as metal catalysts and metal substrates. Example film-forming materials can be the product of a poly-functional epoxide and a nucleophilic ligand having a nonionic metal coordinating structure, or the product of a poly-functional alcohol and an electrophilic ligand having a nonionic metal coordinating structure.

BACKGROUND

Coating compositions are used in a variety of applications to coat avariety of substrates, often for protection of the substrate or toimprove adhesion of subsequent coating layers. Typical coatings includeelectrodeposition coatings, primers, sealers, basecoats, clearcoats, andone-coat topcoats. Coating compositions include film-forming materialscontaining one or more resins, which may be polymeric, oligomeric,and/or monomeric materials, that are applied to a substrate by variousmethods, including electrodeposition (or electrocoating), spray coating,dip coating, roll coating, knife coating, and curtain coating. As usedherein, a “resin” refers to one or more polymeric, oligomeric, and/ormonomeric materials; a polymer includes repeating monomer units; anoligomer includes a few repeating monomer units, typically ten or fewer.Various types of film-forming materials are known, including epoxy,acrylic, polyurethane, polycarbonate, polysiloxane, aminoplast, andpolyester resins.

Coating compositions can include a pigment dispersing or grind resin anda principal resin that generally constitutes the major polymeric part ofthe coating film. A grind resin usually includes a film-formingmaterial, with which a pigment paste is made by wetting out pigment,filler, and catalyst, such as a metal catalyst, where the grind resin isblended or mixed with the other materials by milling in, e.g., asandmill, ball mill, attritor, or other equipment. The pigment paste iscombined with the principal resin and, typically, a curing agent. Thegrind resin and the principal resin can include the same, different, ormixtures of various film-forming materials.

The relatively soft film of an applied coating composition can behardened by curing or crosslinking the film through incorporation of acrosslinker or curing agent in the coating composition. The crosslinkercan be chemically reactive toward the polymers, oligomers, and/ormonomeric compounds of the resin in the coating composition, therebycovalently joining the film-forming units together into a crosslinkedfilm. Typical crosslinkers are activated (e.g., unblocked) using heatduring a curing step and/or by exposure to actinic radiation. Catalysts,such as metal catalysts, can be used to facilitate thermal activation ofthe crosslinker and the reaction of the crosslinker with the resin. Forexample, inclusion of a catalyst such as a metal catalyst can reduce therequisite cure temperature and/or provide for a more complete cure.

Coating compositions can be powder, organic solvent based, or aqueousbased However, it is often desirable to use aqueous based coatings inorder to reduce organic emissions. Such aqueous coating compositionsinclude emulsions and dispersions of cationic, anionic, or nonionicresins, which may be formed via the dispersive properties of the resinsthemselves or with aid of external surfactants

Epoxy-based coatings include polymers, oligomers, and/or monomersprepared by reacting materials with epoxide groups with materials havingfunctional groups such as carboxyl, hydroxyl, and amine groups. Epoxiescan be cured or crosslinked to form hardened coatings by using variouscrosslinkers depending on the functional groups present. For example,hydroxy-functional resin can be cured using isocyanate compounds. Suchcoating compositions are known in the art; e.g., U.S. Pat. Nos.6,852,824; 5,817,733; and 4,761,337.

The electrodeposition process can be anodic or cathodic; typically thearticle to be coated serves as the cathode. Electrodeposition processesare advantageous both economically and environmentally due to the hightransfer efficiency of coating resin to the substrate and the low levelsof organic solvent, if any, that are employed. Another advantage ofelectrocoat compositions and processes is that the applied coatingcomposition forms a uniform and contiguous layer over a variety ofmetallic substrates regardless of shape or configuration. This isespecially advantageous when the coating is applied as an anticorrosivecoating onto a substrate having an irregular surface, such as a motorvehicle body. The even and continuous coating layer formed over allportions of the metallic substrate provides maximum anticorrosioneffectiveness.

Electrocoat baths can comprise an aqueous dispersion or emulsion of afilm-forming material, such as an epoxy resin, having ionicstabilization. A dispersion is typically a two-phase system of one ormore finely divided solids, liquids, or combinations thereof in acontinuous liquid medium such as water or a mixture of water and organiccosolvent. An emulsion is a dispersion of liquid droplets in a liquidmedium, preferably water or a mixture of water and various cosolvents.Accordingly, an emulsion is a type of dispersion.

For automotive or industrial applications, the electrocoat compositionsare formulated to be curable compositions by including a crosslinker.During electrodeposition, a coating composition containing anionically-charged resin is deposited onto a conductive substrate bysubmerging the substrate in an electrocoat bath having dispersed thereinthe charged resin and then applying an electrical potential between thesubstrate and a pole of opposite charge, for example, a stainless steelelectrode. The charged coating particles are plated or deposited ontothe conductive substrate. The coated substrate is then heated to curethe coating.

It is desirable to increase the performance of coating compositions.Particularly, for many applications, improvement in the adhesivestrength of the cured coating film would be beneficial. Furthermore,reducing the cure temperature for crosslinking the coating film wouldsimplify the coating process by reducing the energy and expenserequired. Moreover, lower cure temperatures would be advantageous forapplying coatings to thermally-sensitive substrate materials. Finally,any simplification in the synthesis and preparation of coatingcompositions that reduces time and expense would provide furtheradvantages.

A need, therefore, exists for coating compositions that have bettersubstrate adhesion, reduced cure temperatures, and that are simpler toproduce.

SUMMARY

The present disclosure provides in one embodiment a film-formingmaterial comprising a resin, wherein the resin includes at least onependent group comprising a nonionic metal coordinating structure and atleast one crosslinkable group. The crosslinkable group can be reactivewith a crosslinker, self condensing, reactive with another group on theresin, or addition polymerizable. The resin can be any film-formingresin, such as an epoxy, acrylic, polyurethane, polycarbonate,polysiloxane, aminoplast, or polyester resin and can be a homopolymer orcopolymer.

In certain embodiments, the pendent group comprising a nonionic metalcoordinating structure can be bonded to the resin via an ether linkage.The group reactive with a crosslinker can be an epoxide, hydroxyl,carboxyl, carbamate, or amine group.

In various embodiments, the nonionic metal coordinating structurecomprises a first electron-rich group. The first electron-rich group caninclude an atom such as nitrogen, oxygen, phosphorous, sulfur, silicon,and carbon and can include groups such as ester, ketone, ether,unsaturated carbon, and hydroxyl groups. The nonionic metal coordinatingstructure can further include a second electron-rich functional groupthat is in an alpha- or beta-position relative to the firstelectron-rich functional group. The nonionic metal coordinatingstructure in the film-forming material can coordinate a metal atom ofmaterials including metals and metal compounds, such as metal substratesand metal catalysts.

In some embodiments, a crosslinker for polymerizing a film-formingmaterial comprises an organic compound, such as an alkyl or aromaticcompound, comprising at least two functional groups reactive with afilm-forming resin and at least one pendent group comprising a nonionicmetal coordinating structure.

Embodiments further include methods of producing curable film-formingmaterials and film-forming materials produced by reacting resins andligands having a nonionic metal coordinating structure. For example,film-forming materials can be the product of a reaction between a resin,wherein the resin has at least one group reactive with a nucleophile,and a nucleophilic ligand. Film-forming materials can also be theproduct of a reaction of a resin, wherein the resin has at least onegroup reactive with an electrophile, and an electrophilic ligand.

In various other embodiments, methods of producing a coated substrateare provided. Methods of producing a coated substrate include preparinga coating composition comprising a crosslinker and a film-formingmaterial, wherein one of the crosslinker and the film-forming materialcomprises a nonionic metal coordinating structure; and applying thecoating composition to the substrate.

Some embodiments of the present disclosure include methods of producingcoating compositions. Coating compositions include a film-formingmaterial having a pendent nonionic metal coordinating structure and acrosslinkable group. The film-forming material may be formed by areaction mixture comprising a resin and a ligand having a nonionic metalcoordinating structure. When the film-forming material is notself-crosslinking, the coating composition can include a crosslinkerthat is combined with the film-forming material to produce a coatingcomposition. Various embodiments include coating compositions thatfurther comprise forming an ionizable group on the film-formingmaterial. Also disclosed are methods and coating compositions forelectrodeposition.

In other embodiments, methods of producing a coated substrate areprovided. A coating composition is prepared comprising a crosslinkablefilm-forming material with a ligand having a nonionic metal coordinatingstructure and a crosslinker. The coating composition can be applied to asubstrate. In some embodiments, application of the coating compositionto an electrically conductive substrate is by electrodeposition. Theapplied coating is cured.

The present disclosure affords various benefits including the additionof nonionic metal coordinating groups into the resin and/orincorporation of nonionic metal coordinating groups into thecrosslinker. The technology described herein provides incorporatingnonionic metal coordinating ligands at one or more sites along thepolymeric backbone of a resin and/or incorporating metal coordinatinggroups at one or plural terminal positions on a resin, thereby forming afilm-forming material comprising groups that coordinate metals and metalcompounds. This process can provide a coating composition that has afilm-forming material that presents metal coordinating sites to interactwith metals or metal-containing compounds

The film-forming materials of the present disclosure provide anadvantage in that the film-forming materials can coordinate metalcatalysts to reduce the requisite cure temperature of the coatingcomposition and/or provide for more complete curing. For example,embodiments of the present disclosure enable liquid organo-metallicsalts to be added directly to the aqueous coating composition to formresin and metal catalyst complexes so that metal catalysts ororgano-metallics, such as metal carboxylate complexes, do not have to beadded to the electrodeposition bath. Metal compounds added to theelectrodeposition bath can present compatibility issues with the coatingformulation and potentially lead to coating defects, for example, due tohydrolysis of metal carboxylates. Or, in the case of metal oxidecatalysts, the present process has advantages since it obviates a needto incorporate metal oxides into a coating composition via a grindingprocess.

Another advantage of the present film-forming materials is that themetal coordinating structures employed are nonionic metal coordinatingstructures. Consequently, aqueous electrodepositable coatingcompositions formed using the film-forming materials of the presentdisclosure have reduced or substantially no compatibility issues withsalting agents. Conversely, resins having ionic metal coordinatinggroups can compromise the effectiveness of salting agents in forming anelectrocoating composition, and the salting agents can in turncompromise the coordination of the metal catalysts.

The film-forming materials of the present invention can also providebetter adhesion to and protection of a metal substrate. Without wishingto be bound by theory, it is believed that the nonionic metalcoordinating structures in the film-forming materials can interact withthe metal substrate surface to enhance adhesion of the polymeric filmthereto. Furthermore, coating compositions according to the presentdisclosure can be formulated such that some of the metal coordinatingstructures are complexed with metal catalysts to enhance curing, whileother metal coordinating structures are free to interact with the metalsubstrate to enhance adhesion.

“A” and “an” as used herein indicate “at least one” of the item ispresent; a plurality of such items may be present, when possible.“About” when applied to values indicates that the calculation or themeasurement allows some slight imprecision in the value (with someapproach to exactness in the value; approximately or reasonably close tothe value; nearly). If, for some reason, the imprecision provided by“about” is not otherwise understood in the art with this ordinarymeaning, then “about” as used herein indicates at least variations thatmay arise from ordinary methods of measuring or using such parameters.

DRAWINGS

The drawings described herein are for illustration purposes only and arenot intended to limit the scope of the present disclosure in any way.

FIG. 1 is a graphical representation of scribe creep from CorrosionTests using metal substrates coated with exemplary coating compositionsincluding metal coordinating and film-forming materials constructed inaccordance with the present teachings.

DETAILED DESCRIPTION

Further areas of applicability and advantages will become apparent fromthe following description. It should be understood that the descriptionand specific examples, while exemplifying various embodiments of theinvention, are intended for purposes of illustration and are notintended to limit the scope of the invention.

In a first embodiment, a film-forming material can comprise acrosslinkable resin, wherein the resin includes at least one pendentgroup comprising a nonionic metal coordinating structure and acrosslinkable functionality selected from at least one group reactivewith a crosslinker, at least one self-condensing group, and at least onegroup curable with actinic radiation. The film-forming material can beprepared by reacting a resin, wherein the resin has at least one groupreactive with a nucleophile, and a nucleophilic ligand; or, by reactinga resin, wherein the resin has at least one group reactive with anelectrophile, and an electrophilic ligand. The nucleophilic ligand andthe electrophilic ligand each include a metal coordinating structure.Coating compositions include the film-forming materials described inthis disclosure, methods of coating substrates include application ofcoating compositions having these film-forming materials, and coatedsubstrates have coatings prepared from such coating compositions.

In one embodiment, the film-forming material comprises a resin thatincludes at least one pendent group comprising a nonionic metalcoordinating structure and at least one group reactive with acrosslinker. The resin can include one or more polymeric, oligomeric,and/or monomeric materials. The film-forming material can includevarious resins, such as epoxy, acrylic, polyurethane, polycarbonate,polysiloxane, polyvinyl, polyether, aminoplast, and polyester resins,and can include mixtures thereof. In these embodiments where the resinis a polymer, it can be a homopolymer or a copolymer. Copolymers havetwo or more types of repeating units.

In some embodiments, the pendent group comprising a nonionic metalcoordinating structure is bonded to the resin via various linkagesresulting from the reaction of various functional groups. These variouslinkages include ester, amine, urethane, and ether bonds, among others.Exemplary reactions of functional groups to produce these linkagesinclude: epoxide reacted with acid resulting in an ester linkage;epoxide reacted with amine resulting in an amine linkage; hydroxylreacted with isocyanate resulting in a urethane linkage; hydroxylreacted with anhydride resulting in an ester linkage; epoxide reactedwith hydroxyl resulting in an ether linkage; and other types of linkagesgenerally used in forming coating resins. The at least one groupreactive with a crosslinker can be an epoxide, hydroxyl, carboxyl, oramine group.

In some embodiments, a film-forming material comprises an epoxy resincomprising the formula:

wherein, X¹ and X² are independently hydrogen, hydroxyl, epoxide, oramine functional monovalent radicals; each R¹ and R² is independentlyalkylene or arylene divalent radicals; R³ is an alkylene or arylenedivalent radical comprising a nonionic metal coordinating structure; nis a number from 1 to about 12; m is a number from 0 to about 12; and pis a number from 1 to about 12.

In some embodiments, the alkyl or aromatic divalent radicals denoted byR¹ and R² can be 2,2-diphenylpropylene divalent radicals. Exemplary R³alkylene or arylene divalent radicals comprising a nonionic metalcoordinating structure include divalent radicals (where two bondedhydrogen atoms are removed) of ethyl 2-hydroxybenzoate,4-hydroxy-1-(4-hydroxyphenyl)pentan-2-one, and1-(2-hydroxy-6-methoxyphenyl)ethanone.

Furthermore, in cases where n>1 and/or m>1, two or more2,2-diphenylpropylene radicals can be covalently bonded to each other.For example, in some embodiments where n and/or m>1, R¹ and R² of theresin can comprise part of the product formed by the reaction ofdiglycidyl ether of bisphenol A (“G”) and bisphenol A (“B”), whichresults in repeats of the formula -G-B-. Embodiments further includepermutations wherein n and/or m is a number from 1 to about 12, thatresult in repeating units such as -G-B-G-, -G-B-G-B-, -G-B-G-B-G-, andso on.

In some embodiments, X¹ and X² are independently hydrogen, hydroxyl,epoxide, or amine functional monovalent radicals. Embodiments of resinswhere X¹ and/or X² are amine monovalent radicals can include epoxyresins capped with an amine, for example, by reacting anamine-containing compound with an epoxide group. Exemplary cappingcompounds can include ammonia or amines such as dimethylethanolamine,aminomethylpropanol, methylethanolamine, diethanolamine,diethylethanolamine, dimethylaminopropylamine, the diketamine derivativeof diethylenetriamine, and mixtures thereof. A cathodic electrocoatingcomposition is formed by salting the resin and dispersing it in water.

It should be noted that in some embodiments, such as for example, liquidepoxy coating compositions, the overall molecular weight of thefilm-forming material will affect the liquid phase properties, such asthe viscosity of the coating composition. Consequently, the molecularweight (and corresponding viscosity) of the resin can be adjusted asrequired by changing the number of repeating portions in the resin byvarying the values of n, m, and p in the above formula. For example,film-forming materials can include from one to about twelve unitsdenoted by both n and p and from zero to about twelve units denoted bym.

In some embodiments, the resin is an acrylic polymer, which can beprepared from monomers such as methyl acrylate, acrylic acid,methacrylic acid, methyl methacrylate, butyl methacrylate, cyclohexylmethacrylate, and the like. The acrylic polymer comprises a functionalgroup which is a hydroxyl, amino or epoxy group that is reactive with acuring agent (i.e., crosslinker). The functional group can beincorporated into the ester portion of the acrylic monomer. For example,hydroxyl-functional acrylic copolymers may be formed by polymerizationusing various acrylate and methacrylate monomers, including but notlimited to, hydroxyethyl acrylate, hydroxybutyl acrylate, hydroxybutylmethacrylate, or hydroxypropyl acrylate; amino-functional acryliccopolymers by polymerization with t-butylaminoethyl methacrylate andt-butylaminoethylacrylate; and epoxy-functional acrylic copolymers byreaction with glycidyl acrylate, glycidyl methacrylate, or allylglycidyl ether.

Other ethylenically unsaturated monomers that may be used in forming theacrylic copolymer having reactive functionality include esters ornitriles or amides of alpha-, beta-ethylenically unsaturatedmonocarboxylic acids containing 3 to 5 carbon atoms; vinyl esters, vinylethers, vinyl ketones, vinyl amides, and vinyl compounds of aromaticsand heterocycles. Representative examples include acrylic andmethacrylic acid amides and aminoalkyl amides; acrylonitrile andmethacrylonitriles; esters of acrylic and methacrylic acid, includingthose with saturated aliphatic and cycloaliphatic alcohols containing 1to 20 carbon atoms such as methyl, ethyl, propyl, butyl, 2-ethylhexyl,isobutyl, isopropyl, cyclohexyl, tetrahydrofurfuryl, and isobornylacrylates and methacrylates; esters of fumaric, maleic, and itaconicacids, like maleic acid dimethyl ester and maleic acid monohexyl ester;vinyl acetate, vinyl propionate, vinyl ethyl ether, and vinyl ethylketone; styrene, α-methyl styrene, vinyl toluene, and 2-vinylpyrrolidone.

Acrylic copolymers may be prepared by using conventional techniques,such as free radical polymerization, cationic polymerization, or anionicpolymerization, in, for example, a batch, semi-batch, or continuous feedprocess. For instance, the polymerization may be carried out by heatingthe ethylenically unsaturated monomers in bulk or in solution in thepresence of a free radical source, such as an organic peroxide or azocompound and, optionally, a chain transfer agent, in a batch orcontinuous feed reactor. Alternatively, the monomers and initiator(s)may be fed into the heated reactor at a controlled rate in a semi-batchprocess. Where the reaction is carried out in a solution polymerizationprocess, the solvent should preferably be removed after thepolymerization is completed. Preferably, the polymerization is carriedout in the absence of any solvent.

Typical free radical sources are organic peroxides such as dialkylperoxides, peroxyesters, peroxydicarbonates, diacyl peroxides,hydroperoxides, and peroxyketals; and azo compounds such as2,2′-azobis(2-methylbutanenitrile) and1,1′-azobis(cycohexanecarbonitrile). Typical chain transfer agents aremercaptans such as octyl mercaptan, n- or tert-dodecyl mercaptan,thiosalicyclic acid, mercaptoacetic acid, and mercaptoethanol;halogenated compounds, and dimeric alpha-methyl styrene. The freeradical polymerization is usually carried out at temperatures from about20° C. to about 250° C., preferably from 90° C. to 170° C. The reactionis carried out according to conventional methods to produce a solidacrylic copolymer.

Acrylic resins can have a hydroxyl value of 20 to 120, preferablybetween 50 and 100, and a number average molecular weight of 3,000 to35,000, preferably between 10,000 and 20,000. A typical acrylic polymeris a hydroxy functional acrylic polyol. In some embodiments, an acrylicresin can be used to form an electrocoating composition. A cathodicelectrocoating composition may be formed by copolymerizing anamine-functional ethyleneically unsaturated monomer. The amine is saltedand dispersed in water.

In some embodiments, the resin is a polyester resin. Poly-functionalacid or anhydride compounds can be reacted with polyfunctional alcoholsto form the polyester, and include alkyl, alkylene, aralkylene, andaromatic compounds. Typical compounds include dicarboxylic acids andanhydrides; however, acids or anhydrides with higher functionality mayalso be used. If tri-functional compounds or compounds of higherfunctionality are used, these may be used in mixture withmono-functional carboxylic acids or anhydrides of monocarboxylic acids,such as versatic acid, fatty acids, or neodecanoic acid.

Illustrative examples of acid or anhydride functional compounds suitablefor forming the polyester groups or anhydrides of such compounds includephthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid,hexahydrophthalic acid, tetrachlorophthalic anhydride, hexahydrophthalicanhydride, pyromellitic anhydride, succinic acid, azeleic acid, adipicacid, 1,4-cyclohexanedicarboxylic acid, citric acid, and trimelliticanhydride

The polyol component used to make the polyester resin has a hydroxylfunctionality of at least 2. The polyol component may contain mono-,di-, and tri-functional alcohols, as well as alcohols of higherfunctionality. Diols are a typical polyol component. Alcohols withhigher functionality may be used where some branching of the polyesteris desired, and mixtures of diols and triols can be used as the polyolcomponent. However, in some cases, highly branched polyesters are notdesirable due to effects on the coating, such as decreased flow, andundesirable effects on the cured film, such as diminished chipresistance and smoothness.

Examples of useful polyols include, but are not limited to, ethyleneglycol, diethylene glycol, triethylene glycol, propylene glycol,dipropylene glycol, butylene glycol, glycerine, trimethylolpropane,trimethylolethane, pentaerythritol, neopentyl glycol,2,2,4-trimethyl-1,3-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, and ethoxylated bisphenols.

Methods of making polyester resins are well-known. Polyesters aretypically formed by heating together the polyol and poly-functional acidcomponents, with or without catalysis, while removing the by-product ofwater in order to drive the reaction to completion. A small amount of asolvent, such as toluene, may be added in order to remove the waterazeotropically. If added, such solvent is typically removed from thepolyester product before the coating formulation is begun.

In some embodiments, the resin can be a polyurethane resin.Polyurethanes can be formed from two components, where the firstincludes compounds containing isocyanate-reactive groups, preferablyhydroxyl groups, which are at least difunctional for the purposes of theisocyanate-addition reaction. The second component includes at least onepolyisocyanate compound.

The polyol component must be at least difunctional for the purpose ofthe polymerization reaction. These compounds generally have an averagefunctionality of about two to eight, preferably about two to four. Thesecompounds generally have a molecular weight of from about 60 to about10,000, preferably from 400 to about 8,000. However, it is also possibleto use low molecular weight compounds having molecular weights below400. The only requirement is that the compounds used should not bevolatile under the heating conditions, if any, used to cure thecompositions.

Preferred macromonomer compounds containing isocyanate-reactive hydrogenatoms are the known polyester polyols, polyether polyols, polyhydroxypolyacrylates and polycarbonates containing hydroxyl groups. In additionto these polyhydroxl compounds, it is also possible to use polyhydroxypolyacetals, polyhydroxy polyester amides, polythioethers containingterminal hydroxyl groups or sulfhydryl groups or at least difunctionalcompounds containing amino groups, thiol groups or carboxyl groups.Mixtures of the compounds containing isocyanate-reactive hydrogen atomsmay also be used. Other exemplary hydroxyl containing compounds can befound in U.S. Pat. No. 4,439,593 issued on Mar. 27, 1984, which ishereby incorporated by reference.

The film-forming material according to the first embodiment includes anonionic metal coordinating structure. A nonionic metal coordinatingstructure can include aromatic and/or alkyl groups and can include anatom or group of atoms that is electron-rich but without a net electriccharge (i.e., nonionic). For example, the nonionic metal coordinatingstructure can include one or more atoms or groups of atoms that havehigh electron density and comprise electron-rich functional groups.Exemplary electron-rich functional groups can include one or more of thefollowing: nitrogen atoms, oxygen atoms, phosphorous atoms, sulfuratoms, silicon atoms, and carbon atoms having unsaturated bonds; esters;ketones; ethers; hydroxyls; carboxylates; alcoholic ketones; and cyclicesters. Other exemplary nonionic metal coordinating structures caninclude two electron-rich functional groups, one in an alpha- orbeta-position relative to the other, selected from hydroxyls, carbonyls,esters, ethers, and combinations thereof. An exemplary nonionic metalcoordinating structure having two electron-rich functional groupsincludes beta-hydroxy esters.

In some embodiments, the film-forming material further comprises one ormore metals or metal containing compounds that are coordinated by thenonionic metal coordinating structure. Film-forming materials cantherefore coordinate one or more metals, including metal catalysts thatimprove the cure response of the film-forming material when used in acoating composition. Metal materials can include those selected from agroup consisting of M, MO, M₂O₃, M(OH)_(n), R_(x)MO, and combinationsthereof; wherein, n is an integer satisfying the valency of M; R is analkyl or aromatic group; and x is an integer from 1 to 6. In somepreferred embodiments, M is selected from the group consisting of Al,Bi, Ce, Cu, Fe, Pb, Sn, Sb, Ti, Y, Zn, and Zr. Exemplary metal catalystscan include dibutyl tin oxide, dibutyl tin dilaurate, zinc oxide,bismuth oxide, tin oxide, yttrium oxide, copper oxide, and combinationsthereof.

Embodiments of the present disclosure include crosslinker (i.e., curingagent) compounds having nonionic metal coordinating structures. Forexample, in some embodiments a crosslinker for a film-forming materialcomprises an alkyl or aromatic compound comprising at least twofunctional groups reactive with a film-forming resin and at least onependent group comprising a nonionic metal coordinating structure.Functional groups reactive with a film-forming resin include isocyanate,blocked isocyanate, uretdione, epoxide, hydroxyl, carboxyl, carbamate,aldehyde, amide, and amine groups. Crosslinkers having nonionic metalcoordinating structures can coordinate metals or metal compounds, suchas metal catalysts. Furthermore, these crosslinkers can be mixed withthe film-forming materials of the present disclosure and/or with otherresins to form coating compositions which can be used to coatsubstrates. For example, a method of producing a coated substratecomprises preparing a coating composition comprising a crosslinker and afilm-forming material, wherein one of the crosslinker and thefilm-forming material comprises a nonionic metal coordinating structure;and applying the coating composition to the substrate.

In various embodiments, the nonionic metal coordinating structure of thefilm-forming material can be formed in situ during the resin synthesis.These embodiments include film-forming materials, and populations ofvarious film-forming materials, having metal coordination sites situatedalong the polymeric backbone (i.e., interspersed with the repeatingunits of the polymer) and/or at the terminal ends of the resinmolecules. Film-forming materials of the present disclosure can besynthesized by various reaction schemes to incorporate a nonionic metalcoordinating structure into the resin during the process of the resinbackbone synthesis. For example, various embodiments include anucleophilic reaction scheme and various other embodiments include anelectrophilic reaction scheme.

The resin or crosslinker is functionalized using a ligand where theligand can comprise the nonionic metal coordinating structure. Forexample, various nucleophilic ligands can react with a resin that has atleast one group reactive with a nucleophile, or various electrophilicligands can react with a resin that has at least one group reactive withan electrophile. The ligands containing the nonionic metal coordinatingstructure can be aromatic or nonaromatic and have a reactive site(either nucleophilic or electrophilic) and one or more electron-richsites (i.e., the nonionic metal coordinating structure).

In other various embodiments, a film-forming material comprises aproduct of a reaction of a poly-functional epoxide and a nucleophilicligand. Such embodiments include products of the following exemplaryreaction scheme using an epoxy resin based on the product of bisphenol Aand the diglycidyl ether of bisphenol A.

In various embodiments, a film-forming material comprises a product of areaction of a resin, wherein the resin has at least one group reactivewith a nucleophile, and a nucleophilic ligand, wherein the nucleophilicligand has the formula:

X³—R⁴—X⁴

wherein, particularly, at least one of X³ and X⁴ is reactive with theresin, X³ is a hydroxyl or carboxyl monovalent radical; R⁴ is an alkylor aromatic divalent radical having a molecular weight from about 90g/mol to about 5000 g/mol and a nonionic metal coordinating structure;and X⁴ is a hydrogen, hydroxyl, or carboxyl monovalent radical.

Thus, nucleophilic ligands can have one or two nucleophilic reactivesites. For example, X³ can provide a first nucleophilic reactive site inthe form of a hydroxyl or carboxyl group, while X⁴ can be hydrogen orcan provide a second nucleophilic reactive site in the form of ahydroxyl or carboxyl group. As such, embodiments of nucleophilic ligandscan be used for terminal addition only (i.e., where X⁴ is hydrogen) orcan be used for terminal addition and/or reaction with another group(i.e., where X⁴ is a hydroxyl or carboxyl group), such as anotherepoxide group, isocyanate group, hydroxyl group, anhydride, and othergroups reactive with hydroxyl or carboxyl groups. Thus, film-formingmaterials produced from the reaction can have terminal and/or pendentnonionic metal coordinating structures within the resin. In someembodiments, the nucleophilic ligand is selected from a group consistingof ethyl salicylate, ethylparaben,4-hydroxy-1-(4-hydroxyphenyl)pentan-2-one,1-(2-hydroxy-6-methoxyphenyl)ethanone, 1,5-dihydroxyanthraquinone;apigenin; baicalein; 2,2′-bipyridine-3,3′-diol;N,N′-bis(salicylidene)ethylenediamine;4-(tert-butyldimethylsiloxy)phenol;2-carbethoxy-5,7-dihydroxy-4′-methoxyisoflavone;1,8-dihydroxyanthraquinone; 6,7-dihydroxyflavone; chrysophanic acid;5,7-dihydroxyphenylcoumarin; ellagic acid; emodin; 2,3-dinitrophenol;2,4-dinitrophenol; fisetin; 7-hydroxy-4-methyl-8-nitrocoumarin; andcombinations thereof.

Embodiments of the reaction can further include other reactants,including other nucleophiles, capping agents, terminating agents, metalcatalysts, and combinations thereof. Exemplary molecules includebisphenol A, bisphenol F, diols, amines, phenol, and metals and metalcatalysts. In some embodiments, the resin can be a poly-functionalepoxide such as diglycidyl ether of bisphenol A. In other embodiments,the resin can be an acrylic, polyurethane, polycarbonate, polysiloxane,polyvinyl, polyether, aminoplast, or polyester resin. Also included aremixtures of different resins.

In some embodiments, other nucleophiles can be included in the reactionin addition to the nucleophilic ligand. This allows the nucleophilicligand and other nucleophiles to react with the resin to form variousmixtures of film-forming materials. For example, such a reaction canresult in mixed populations of film-forming materials. To illustrate,diglycidyl ether of bisphenol A, bisphenol A, and a nucleophilic ligandcan react in order to form various film-forming materials where theligand is incorporated in various positions in the resulting polymer andthe film-forming material can contain populations of various polymerlengths.

In addition, in some embodiments the reaction can be performed usingmultiple steps, for example, where the resin (e.g., diglycidyl ether ofbisphenol A) and another nucleophile (e.g., bisphenol A) are reactedfirst, then the nucleophilic ligand is added, and vice versa. Thus,these embodiments allow the length, proportion of different regions, andthe extent of ligand incorporated in the film-forming material to beadjusted.

In other various embodiments, a film-forming material comprises aproduct of a reaction of a resin, wherein the resin has at least onegroup reactive with an electrophile, and an electrophilic ligand. Suchembodiments include products of the following exemplary reaction scheme:

In some embodiments, a film-forming material comprises a product of areaction of a resin, wherein the resin has at least one group reactivewith an electrophile, and an electrophilic ligand, wherein theelectrophilic ligand has the formula:

X⁵—R⁵—X⁶

wherein, X⁵ is an epoxide or halide monovalent radical; R⁵ is analkylene or arylene divalent radical, preferably having a molecularweight from about 90 g/mol to about 5000 g/mol, and a nonionic metalcoordinating structure; and X⁶ is a hydrogen, epoxide, or halidemonovalent radical.

Thus, electrophilic ligands can have one or two electrophilic reactivesites. For example, X⁵ can provide a first electrophilic reactive sitein the form of an epoxide or halide group, while X⁶ can be hydrogen orX⁶ can provide a second electrophilic reactive site in the form of anepoxide or halide group. As such, embodiments of electrophilic ligandscan be used for terminal addition only (i.e., where X⁶ is hydrogen) orcan be used for terminal addition and/or reaction with another group.Groups reactive with epoxide or halide of the ligand that can be on theresin or reactants in forming the resin include, without limitation,primary and secondary amine groups and carboxyl and hydroxyl groups.Thus, film-forming materials produced from the reaction can haveterminal and/or pendent nonionic metal coordinating structures withinthe resin. In some embodiments, the electrophilic ligand is selectedfrom a group consisting of 3-methyl-1-(oxiran-2-yl)but-3-en-2-one, ethylphenylglycidate, tert-butyldimethylsilyl gkycidyl ether; diethoxy(3-glycidyloxypropyl)methylsilane; diglycidyl-1,2-cyclohexanedicarboxylate;3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate;3,4-epoxytetrahydrothiophene-1,1-dioxide; ethyl-2,3-epoxypropanate;3-glycidopropyldimethoxymethylsilane; glycidyl methacrylate;glycidyl-3-nitrobenzenesulfonate; glycidyl 4-nitrobenzoate;(3-glyloxypropyl)trimethoxysilane; glycidyl tosylate; and combinationsthereof.

Embodiments of the reaction can further include other reactants,including other electrophiles, capping agents, terminating agents, metalcatalysts, and combinations thereof. Exemplary molecules includebisphenol A, bisphenol F, polyols, polyamines, polycarboxylic acids,phenol, and metals and metal catalysts as described elsewhere herein. Insome embodiments, the resin can be a poly-functional alcohol such asbisphenol A. In other embodiments, the resin can be an acrylic,polyurethane, polycarbonate, polysiloxane, polyvinyl, polyether,aminoplast, or polyester resin. Also included are mixtures of differentresins.

In some embodiments, other electrophiles, in addition to theelectrophilic ligand, can be included in the reaction. This allows theelectrophilic ligand and other electrophiles to react with the resin toform various mixtures of film-forming materials. For example, such areaction can result in mixed populations of film-forming materials. Toillustrate, in the case of forming an epoxy, diglycidyl ether ofbisphenol A, bisphenol A, and the electrophilic ligand can react to formvarious film-forming materials where the ligand is incorporated invarious positions in the resulting polymer and the film-forming materialcan contain populations of various polymer lengths.

Furthermore, the reaction can be performed in multiple steps, forexample, where the resin (e.g., bisphenol A) and the other electrophile(e.g., diglycidyl ether of bisphenol A) are reacted first, then theelectrophilic ligand is added, and vice versa. Thus, these embodimentsallow the length, proportion of monomers with different functionalities,and number of monomer units bearing the ligand in the film-formingmaterial to be adjusted.

In addition to nucleophilic and electrophilic addition techniques, thepresent disclosure includes various embodiments where the nucleophilicor electrophilic ligand can be a chain terminator or a chain propagatoror a combination thereof in the polymerization reaction. This can beaccomplished by using mono-functional molecules (for chain termination)and/or poly-functional molecules (for chain propagation).

The amount of nucleophilic or electrophilic ligand in the reaction canalso be optimized for specific performance characteristics. In someembodiments, it is not necessary incorporate the ligand throughout thebackbone of the film-forming material. In fact, in some embodiments,most of the units in the polymer backbone do not contain incorporatedligand. The amount of incorporated ligand can be adjusted to provideenough ligand having a nonionic metal coordinating structure tocoordinate with a metal and/or metal catalyst so that sufficient cureresults and/or desired adhesion characteristics are realized.

In some embodiments, various components in the reaction used to form afilm-forming material are adjusted to change the amount of ligand thatis incorporated and/or the number of repeating units in the resinpolymer. Embodiments include replacing from about 1% equivalent weightor less, to essentially replacing all of the terminal reactant (i.e., apolymer chain terminating reactant) or capping group, or the propagationgroup (i.e., a polymer chain propagating reactant) with ligand. Someembodiments include replacing from about 1% to about 50% equivalentweight of the terminal reactant or propagation group with ligand, and inother embodiments from about 5% to about 15% equivalent weight is used.

The amount of ligand used in the reaction can depend on whether aterminal addition product is desired or whether a polymer chainpropagating ligand is to be extensively incorporated throughout thereaction product. Replacing a small amount (e.g., about 5% equivalentweight) of the terminal reactant or the propagation group in thereaction leads to sufficient incorporation of the ligand (e.g., anucleophilic or electrophilic ligand) having a nonionic metalcoordinating structure, thereby resulting in a film-forming materialcapable of sufficiently coordinating a metal catalyst. For example, asshown in the exemplary nucleophilic reaction scheme, some of the cappingphenol can be replaced with the nucleophilic ligand accounting for about5% equivalent weight of the total composition of the polymerized resin,where the rest of the reaction can comprise phenol, poly-functionalepoxide, and bisphenol A. In various other embodiments, substitution ofmore than 15% equivalent weight of the terminal or the propagation groupcan lead to a film-forming material incorporating a greater number ofnonionic metal coordinating structures that afford increased adhesion ofthe coating to the metal substrate and/or coordination of metalcatalyst.

In some reaction embodiments, the ligand can be used in excess so thatall, or substantially all, of the ligand reactive groups, e.g., theterminal groups, of the resulting film-forming material include theligand molecule. In other cases, the ligand can be incorporatedthroughout the backbone of the film-forming material. Such film-formingmaterials contain many nonionic metal coordinating structures and cancoordinate metal catalyst and/or improve adhesion of the resin to ametal substrate.

In some embodiments, a film-forming material comprising a product of thereactions described herein can include a mixed population of resinmolecules. For example, these reactions can result in film-formingmaterial products consisting of fractions of various film-formingmaterials with different values for n, m, and p. These film-formingmaterials can result from variations in the rate of propagation andtermination events in the reaction and/or by adding various reactants instages.

It should be noted that the film-forming material comprising a productof the various reactions described herein differs from other resins andmethods in which a ligand having an ionic metal coordinating structureis grafted onto a resin backbone after the polymerization process byaddition of an anhydride, as described in U.S. patent application Ser.No. 11/278,030 filed Mar. 30, 2006. First, the present disclosure can beperformed in a single synthesis step, and does not require a two-stepgrafting reaction. Second, the nonionic metal coordinating structures ofthe present disclosure do not have a net electrical charge, unlike ionicmetal coordination groups.

The film-forming materials of the present disclosure can be used toproduce coating compositions comprising the film-forming material formedby a reaction mixture comprising a resin, wherein the resin has at leastone group reactive with a nucleophile, and a nucleophilic ligand andcombining a crosslinker and the film-forming material, or by a reactionmixture comprising a resin, wherein the resin has at least one groupreactive with an electrophile, and an electrophilic ligand and combininga crosslinker and the film-forming material. These embodiments caninclude the various poly-functional epoxides, nucleophilic ligands,poly-functional alcohols, and electrophilic ligands as described forepoxy-based resins. For example, the nucleophilic and electrophilicligands and film-forming materials include the various nonionic metalcoordinating structures as described elsewhere herein.

Coating compositions can also be produced using acrylic, polyurethane,polycarbonate, polysiloxane, aminoplast, and/or polyester resins, forexample. These various resins can be formed by reactions of appropriatefunctional groups, as is known in the art, to produce the resin bondlinkages. Such reactions include: epoxide reacted with acid resulting inan ester linkage; epoxide reacted with amine resulting in an aminelinkage; hydroxyl reacted with isocyanate resulting in a urethanelinkage; hydroxyl reacted with anhydride resulting in an ester linkage;epoxide reacted with hydroxyl resulting in an ether linkage; and othertypes of linkages generally used in forming coating resins. Ligandshaving nonionic metal coordinating structures are incorporated intothese resins using these reactive functional group pairings. Theresulting film-forming resin contains a crosslinkable functionality,which can be a group reactive with a crosslinker, a self-condensinggroup, and/or a group curable with actinic radiation. Exemplaryfunctional groups reactive with the film-forming resin includeisocyanate, blocked isocyanate, uretdione, epoxide, hydroxyl, carboxyl,carbamate, aldehyde, amide, and amine groups.

In some embodiments, the film-forming material can comprise a vinyl oracrylic resin, wherein the vinyl resin has at least one pendent groupcomprising a nonionic metal coordinating structure and at least onegroup reactive with a crosslinker. The vinyl resin having nonionic metalcoordinating structures can be formed by including a compound having anunsaturated carbon bond and a nonionic metal coordinating structure inthe resin synthesis. Suitable compounds for incorporation duringaddition polymerization can include the following:4-allyl-1,2-dimethoxybenzene; 2-allyl-2-methyl-1,3-cyclopentanedione;2-allyloxytetrahydropyran; allylphenyl carbonate; 3-allylrhodanine;allyltrimethoxysilane; itaconic anhydride; and combinations thereof.

In various embodiments of producing a coating composition, thefilm-forming materials of the present disclosure can be the solefilm-forming resin, form a population of resins, or can be combined withadditional resins. As mentioned, the film-forming materials can be usedas a grind resin and/or a principal resin and/or crosslinker. The sameresin can be used in preparing the pigment dispersion and the principalresin, or mixtures of various resins can be used to form a coatingcomposition. In a pigmented composition, the grind resin and theprincipal resin can be combined in forming a coating compositioncontaining film-forming material(s) according to the present disclosure.

Additional resins can be included with the film-forming materials of thepresent disclosure. For example, suitable additional resins includeepoxy oligomers and polymers, such as polymers and oligomers ofpolyglycidyl ethers of polyhydric phenols such as bisphenol A. These canbe produced by etherification of a polyphenol with an epihalohydrin ordihalohydrin such as epichlorohydrin or dichlorohydrin in the presenceof alkali. Suitable polyhydric phenols includebis-2,2-(4-hydroxyphenyl)propane, bis-1,1-(4-hydroxyphenyl)ethane,bis(2-hydroxynaphthyl)methane and the like. The polyglycidyl ethers andpolyhydric phenols can be condensed together to form the oligomers orpolymers. Other useful poly-functional epoxide compounds are those madefrom novolak resins or similar poly-hydroxyphenol resins. Also suitableare polyglycidyl ethers of polyhydric alcohols such as ethylene glycol,propylene glycol, diethylene glycol and triethylene glycol. Also usefulare polyglycidyl esters of polycarboxylic acids which are produced bythe reaction of epichlorohydrin or a similar epoxy compound with analiphatic or aromatic polycarboxylic acid such as succinic acid orterepthalic acid.

In some embodiments, these additional resins can be a liquid epoxy thatis the reaction product of diglycidyl ether of bisphenol A and bisphenolA. Examples include modified upgraded epoxy resins having epoxyequivalent weights of approximately 100 to 1200 or more. Suitable liquidepoxies are GY2600, commercially available from Huntsman, and Epon® 828,commercially available from Hexion Specialty Chemicals, Inc. Forexample, epoxy-containing compounds can be reacted withhydroxyl-containing compounds, such as bisphenol A, ethoxylatedbisphenol A, phenol, polyols, or substituted polyols.

These additional resins, including the various film-forming materialshaving nonionic metal coordinating structures, can be further reactedwith an amine containing compound, such as methylaminoethanol, diethanolamine, or the diketamine derivative of diethylenetriamine, to provide asalting site on the resin for use in cathodic electrocoating.Alternatively, quaternium ammonium, sulfonium, or phosphonium sites canbe incorporated. Or, the reaction products can be reacted to provide anacid functionality in order to make anodic electrocoating compositions.

In various embodiments, coating compositions can also include a mixtureof resin compounds with groups reactive with a curing agent. The mixtureof compounds can include more than one type of resin with groupsreactive with a curing agent, a resin mixture with one or moreco-monomers, and more than one resin with at least one co-monomer.

In some embodiments, the present disclosure also includes incorporatinga metal, or a compound with a metal atom, with the film-forming materialto complex the metal with the resin. Metals include the various metalsand metal catalysts already mentioned. The metal can be added to areaction mixture with the nucleophilic or electrophilic ligand having anonionic metal coordinating structure, for example, or the metal canalready be coordinated with the ligand prior to the film-formingmaterial reaction. In such embodiments, the metal catalyst can beincorporated with the ligand prior to curing the resin and crosslinkerto form a cured coating. Alternatively, the metal catalyst can beincorporated with the film-forming material as subpart of a coatingcomposition; for example, the metal catalyst can be added to afilm-forming material used as a grind resin.

The metal catalyst can also be incorporated at other various steps inproducing the film-forming material. In some embodiments, the metalcatalyst is incorporated with the nucleophilic or electrophilic ligandsimultaneously with the step of forming the film-forming material, i.e.,as the film-forming material is formed by the various reaction mixturesdescribed herein. Alternatively, the metal catalyst can be incorporatedwith the film-forming material after the resin is formed and prior tothe reaction of the resin and the crosslinker to form the cured coating.For instance, in some embodiments, a pigment-containing composition maybe incorporated prior to the step of reacting (i.e., curing) the resinand the crosslinker. Coating compositions commonly incorporate suchpigment-containing compositions. The metal catalyst can be incorporatedinto the pigment-containing composition to complex the metal catalystwith the film-forming material.

Embodiments can include one metal catalyst, or in some embodiments, acombination of metal catalysts can be employed. The metal catalysts,such as for example various metal oxides, can be supplied in a milledform having a low particle size (e.g., less than 20 microns, moretypically less than 10 microns) such that no additional grinding isneeded to reduce the particle size of the metal catalyst for effectiveincorporation of the metal catalyst with the film-forming material orligand.

Various embodiments of methods of producing a coating compositioninclude polyisocyanate crosslinkers (i.e., curing agents) capable ofreacting with the film-forming material. Polyisocyanate crosslinkers cancomprise any desired organic polyisocyanate having free isocyanategroups attached to aliphatic, cycloaliphatic, araliphatic and/oraromatic structures. Polyisocyanates can have from 2 to 5 isocyanategroups per molecule. Exemplary isocyanates are described in “Methodender organischen Chemie” [Methods of Organic Chemistry], Houben-Weyl,volume 14/2, 4th Edition, Georg Thieme Verlag, Stuttgart 1963, pages 61to 70, and by W. Siefken, Liebigs Ann. Chem. 562, 75 to 136. Suitableexamples include 1,2-ethylene diisocyanate, 1,4-tetramethylenediisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4- and2,4,4-trimethyl-1,6-hexamethylene diisocyanate, 1,12-dodecanediisocyanate, omega,omega′-diisocyanatodipropyl ether, cyclobutane1,3-diisocyanate, cyclohexane 1,3- and 1,4-diisocyanate, 2,2- and2,6-diisocyanato-1-methylcyclohexane,3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (“isophoronediisocyanate”), 2,5- and3,5-bis(isocyanatomethyl)-8-methyl-1,4-methano-decahydronaphthalene,1,5-, 2,5-, 1,6- and2,6-bis(isocyanatomethyl)-4,7-methanohexahydroindane, 1,5-, 2,5-, 1,6-and 2,6-bis(isocyanato)-4,7-methylhexahydroindane, dicyclohexyl2,4′- and4,4′-diisocyanate, 2,4- and 2,6-hexahydrotolylene diisocyanate, perhydro2,4′- and 4,4′-diphenylmethane diisocyanate,omega,omega′-diisocyanato-1,4-diethylbenzene, 1,3- and 1,4-phenylenediisocyanate, 4,4′-diisocyanatobiphenyl,4,4′-diisocyanato-3,3′-dichlorobiphenyl,4,4′-diisocyanato-3,3′-dimethoxybiphenyl,4,4′-diisocyanato-3,3′-dimethylbiphenyl,4,4′-diisocyanato-3,3′-diphenylbiphenyl, 2,4′- and4,4′-diisocyanatodiphenylmethane, naphthylene-1,5-diisocyanate, tolylenediisocyanates, such as 2,4- and 2,6-tolylene diisocyanate,N,N′-(4,4′-dimethyl-3,3′-diisocyanatodiphenyl)uretdione, m-xylylenediisocyanate, dicyclohexylmethane diisocyanate, tetramethylxylylenediisocyanate, but also triisocyanates, such as2,4,4′-triisocyanatodiphenyl ether, 4,4′,4″-triisocyanatotriphenylmethane. Polyisocyanates can also contain isocyanurate groups and/orbiuret groups and/or allophanate groups and/or urethane groups and/orurea groups. Polyisocyanates containing urethane groups, for example,are obtained by reacting some of the isocyanate groups with polyols, forexample trimethylol propane and glycerol. Examples of suitablecrosslinkers include: unblocked and blocked polyisocyanate compoundssuch as self-blocking uretdione compounds; caprolactam- andoxime-blocked polyisocyanates; isocyanurates of diisocyanates;diioscyanates half-blocked with polyols; and combinations thereof.

Polyisocyanate crosslinkers can further include polymeric MDI, anoligomer of 4,4′-diphenylmethane diisocyanate, or other polyisocyanatethat is blocked with an ethylene glycol ether or a propylene glycolether. Such crosslinkers containing urethane groups can be prepared, forexample, from Lupranate® M20S, or other similar commercially availablematerials. Polyisocyanate compounds are commercially available from,among others, BASF AG, Degussa AG, and Bayer Polymers, LLC.

In some embodiments, thermal curing can include the reaction betweenisocyanate (free or blocked) with an active hydrogen functional groupsuch as a hydroxyl or a primary or secondary amine; or that between anaminoplast and an active hydrogen material such as a carbamate, urea,amide or hydroxyl group; an epoxy with an active hydrogen material suchas an acid, phenol, or amine; a cyclic carbonate with an active hydrogenmaterial such as a primary or secondary amine; a silane (i.e., Si—O—Rwhere R=H, an alkyl or aromatic group, or an ester) with an activehydrogen material, including when the active hydrogen material is Si—OH,as well as mixtures of these crosslinking pairs.

The present disclosure also includes various embodiments wherecrosslinkers or curing agents include nonionic metal coordinatingstructures, where the nonionic metal coordinating structures include thevarious embodiments described elsewhere herein. In some embodiments, amethod of producing a coating composition comprises forming afilm-forming material by the various reaction mixtures described hereinand combining a crosslinker having a nonionic metal coordinatingstructure and the film-forming material. For example, upon curing thesecoating compositions, the resulting cured film can include nonionicmetal coordinating structures incorporated from the film-formingmaterial and/or nonionic metal coordinating structures incorporated fromthe crosslinkers. The nonionic metal coordinating groups may be used toprovide improved adhesion to metal of the coating formed from thecomposition. In some embodiments, the crosslinkers comprising nonionicmetal coordinating structures can be complexed with one or more metalcatalysts prior to forming the coating composition or the metal catalystcan be added after the crosslinker is combined with the film-formingmaterial.

In some embodiments methods of producing a coating composition canfurther comprise forming a salting site on the film-forming material.The film-forming materials can be further reacted with an aminecontaining compound, such as methylaminoethanol, diethanol amine, or thediketamine derivative of diethylenetriamine, to provide a salting siteon the resin for use in cathodic electrocoating. Alternatively,quaternium ammonium, sulfonium, or phosphonium sites can beincorporated. Or, the reaction products can be reacted with an acidfunctionality in order to make anodic electrocoating compositions oranionic aqueous coating compositions.

These salting sites are then reacted, or salted, in forming an aqueousdispersion in forming electrodepositable or other aqueous coatingcompositions, for example. The film-forming material can have basicgroups salted with an acid for use in a cathodic electrocoatingcomposition. This reaction may be termed neutralization or acid-saltedand specifically refers to the reaction of pendent amino or quarternarygroups with an acidic compound in an amount sufficient to neutralizeenough of the basic amino groups to impart water-dispersibility to theresin. Illustrative acid compounds can include phosphoric acid,propionic acid, acetic acid, lactic acid, formic acid, sulfamic acid,alkylsulfonic acids, and citric acid. Or, an acidic resin can be saltedwith a base to make an anodic electrocoating composition. For example,ammonia or amines such as dimethylethanolamine, triethylamine,aminomethylpropanol, methylethanolamine, and diethanolamine can be usedto form an anodic electrocoating composition.

In some embodiments, coating compositions can also include at least oneadditive. Many types of additives are known to be useful in coatingcompositions, including electrocoating compositions. Such additives caninclude various organic solvents, surfactants, dispersants, additives toincrease or reduce gloss, catalysts, pigments, fillers, and saltingagents. Additional additives further include hindered amine lightstabilizers, ultraviolet light absorbers, anti-oxidants, stabilizers,wetting agents, rheology control agents, adhesion promoters, andplasticizers. Such additives are well-known and may be included inamounts typically used for coating compositions.

In some embodiments, the film-forming materials can be used in methodsof producing aqueous coating compositions. The aqueous medium of acoating composition is generally exclusively water, but a minor amountof organic solvent can be used. Examples of useful solvents include,without limitation, ethylene glycol butyl ether, propylene glycol phenylether, propylene glycol propyl ether, propylene glycol butyl ether,diethylene glycol butyl ether, dipropylene glycol methyl ether,propylene glycol monomethyl ether acetate, xylene, N-methylpyrrolidone,methyl isobutyl ketone, mineral spirits, butanol, butyl acetate,tributyl phosphate, dibutyl phthalate, and so on. However, organicsolvent can be avoided to minimize organic volatile emissions from thecoating process.

Examples of suitable surfactants include, without limitation, thedimethylethanolamine salt of dodecylbenzene sulfonic acid, sodiumdioctylsulfosuccinate, ethoxylated nonylphenol, sodium dodecylbenzenesulfonate, the Surfynol® series of surfactants (Air Products andChemicals, Inc.), and Amine-C (Huntsman). Generally, both ionic andnon-ionic surfactants may be used together, and, for example, the amountof surfactant in an electrocoat composition may be from 0 to 2%, basedon the total solids Choice of surfactant can also depend on the coatingmethod. For example, an ionic surfactant should be compatible with theparticular electrocoating composition, whether it is cathodic or anodic.

When the coating composition is a primer composition or pigmentedtopcoat composition, such as a basecoat composition, one or morepigments and/or fillers may be included. Pigments and fillers may beutilized in amounts typically of up to 40% by weight, based on totalweight of the coating composition. The pigments used may be inorganicpigments, including metal oxides, chromates, molybdates, phosphates, andsilicates. Examples of inorganic pigments and fillers that could beemployed are titanium dioxide, barium sulfate, carbon black, ocher,sienna, umber, hematite, limonite, red iron oxide, transparent red ironoxide, black iron oxide, brown iron oxide, chromium oxide green,strontium chromate, zinc phosphate, silicas such as fumed silica,calcium carbonate, talc, barytes, ferric ammonium ferrocyanide (Prussianblue), ultramarine, lead chromate, lead molybdate, and mica flakepigments. Organic pigments may also be used. Examples of useful organicpigments are metallized and non-metallized azo reds, quinacridone redsand violets, perylene reds, copper phthalocyanine blues and greens,carbazole violet, monoarylide and diarylide yellows, benzimidazoloneyellows, tolyl orange, naphthol orange, and the like.

Coating compositions formed according to the methods described hereincan be coated on a substrate by any of a number of techniques well-knownin the art. These can include, for example, spray coating, dip coating,roll coating, curtain coating, knife coating, coil coating, and thelike. In some embodiments, the coating composition of the invention canbe electrodepositable and can be coated onto the substrate byelectrodeposition. The electrodeposited or applied coating layer can becured on the substrate by reaction of the resin and crosslinker.

The coating composition can be electrodeposited as is conventionallyperformed in the art. Electrodeposition includes immersing anelectrically conductive article in an electrocoating bath containing acoating composition of the present invention, connecting the article asthe cathode or anode, preferably as the cathode, depositing a coatingcomposition film on the article using direct current, removing thecoated article from the electrocoating bath, and subjecting thedeposited electrocoated material film to conventional thermal curing,such as baking.

Coating compositions of the present invention are also useful as coilcoatings. Coil coatings are applied to coiled sheet metal stock, such assteel or aluminum, in an economical, high speed process. The coilcoating process results in a high quality, uniform coating with littlewaste of the coating and little generation of organic emissions ascompared to other coating methods, e.g. spray application of a coatingcomposition.

Polyester resins can be used as coil coating compositions and cancomprise a branched polyester and/or an essentially linear polyester anda crosslinking agent. A ligand having a nonionic metal coordinatingstructure can be incorporated into the polyester and/or the crosslinkingagent. The branched polyester can be prepared by condensation of apolyol component and a polyacid component, either of which can furtherinclude the ligand or be reactive with the ligand. The polyestersynthesis may be carried out under suitable, well-known conditions, forexample at temperatures from about 150° C. to about 250° C., with orwithout catalyst (e.g., dibutyl tin oxide, tin chloride, butyl chlorotindihydroxide, or tetrabutyoxytitanate), typically with removal of theby-product water (e.g., by simple distillation, azeotropic distillation,vacuum distillation) to drive the reaction to completion. Thecrosslinking agent can have groups reactive with the hydroxylfunctionality of the polyesters. Suitable crosslinking agents include,without limitation, aminoplasts and isocyanate crosslinking agents. Thecoil coating composition typically further includes a pigment and cancontain other additives and fillers.

Coil coating is a continuous feeding operation, with the end of one coiltypically being joined (e.g., stapled) to the beginning of another coil.The coil is first fed into an accumulator tower and coating is fed intoan exit accumulator tower, with the accumulator towers allowing thecoating operation to continue at constant speed even when intake of thecoil is delayed. For example, coil advancement can be delayed to start anew roll, or for winding of the steel, for example, to cut the steel toend one roll and begin a new roll. The coil is generally cleaned toremove oil or debris, pre-treated, primed with a primer on both sides,baked to cure the primer, quenched to cool the metal, and then coated onat least one side with a topcoat. A separate backer or a differenttopcoat may be applied on the other side. The topcoat is baked andquenched, then fed into the exit accumulator tower and from there isre-rolled.

The coating compositions can be applied onto many different substrates,including metal substrates such as bare steel, phosphated steel,galvanized steel, gold, or aluminum; and non-metallic substrates, suchas plastics and composites including an electrically conductive organiclayer. In electrocoating (e.g., electrodeposition) or electrospray, onlyelectrically conductive substrates are used. The substrate may also beany of these materials having upon it already a layer of anothercoating, such as a layer of an electrodeposited primer, primer surfacer,and/or basecoat, either cured or uncured. When the substrate ismetallic) the film-forming material with the ligand(s) can act toimprove film adhesion to the substrate.

Although various methods of curing may be used, in some embodiments,thermal curing can be used. Generally, thermal curing is effected byheating at a temperature and for a length of time sufficient to causethe reactants (i.e., the film-forming material and crosslinker) to forman insoluble polymeric network. The cure temperature can be from about150° C. to about 200° C. for electrocoating compositions, and the lengthof cure can be about 15 minutes to about 60 minutes. Cure temperaturescan be lower, for example, and in some embodiments can be reduced to160° C. or lower due to the metal catalysts complexed to the nonionicmetal coordination structures in the film-forming materials. Therefore,lower bake temperatures can be used in some instances. Heating can bedone in infrared and/or convection ovens.

A coil coating composition cures at a given peak metal temperature. Thepeak metal temperature can be reached more quickly if the oventemperature is high. Oven temperatures for coil coating generally rangefrom about 220° C. to about 500° C., to obtain peak metal temperaturesof between 180° C. and about 250° C., for dwell times generally rangingfrom about 15 seconds to about 80 seconds. Oven temperatures, peak metaltemperature and dwell times are adjusted according to the coatingcomposition, substrate and level of cure desired. Examples of coilcoating methods are disclosed in U.S. Pat. Nos. 6,897,265; 5,380,816;4,968,775; and 4,734,467, which are hereby incorporated by reference.

The film-forming materials, coating compositions, and methods of thepresent disclosure provide several advantages. For example, pretreatmentof metal surfaces, such as phosphating, can be eliminated due toincreased adhesion and corrosion performance of coating compositionsmade according to present disclosure. Increased adhesion can be due tocomplexes forming between the nonionic metal coordinating sitesincorporated in the film-forming material and the metal substrate.Elimination of the phosphating step in coating a steel substrate cansave time and expense. Furthermore, complexing metal catalysts with thefilm-forming material (or ligands used to form the resin) can improvecure response and catalytic efficiency of the applied coatingcomposition. These improvements can be effected by the proximity of themetal catalyst to the reactive functional groups in the crosslinkingmatrix

The present technology is further described in the following examples.The examples are merely illustrative and do not in any way limit thescope of the technology as described and claimed. All parts given areparts by weight unless otherwise noted. Tradename compounds suitable forpracticing embodiments of the technology may be included, whereapplicable.

EXAMPLES 1A-1D

Examples 1A through 1D are prepared as described and as indicated in therespective tables. Example 1A makes use of phenol as a chain terminatingligand, the ligand is added in less the 5% by weight of the totalcomposition of the polymer. Example 1B makes use of the same ligandmolecule, in this case the terminal group is replaced withethylphenylglycidate and the amount of bisphenol A is increased to leavethe same equivalents of unreacted epoxy after the polymer upgradereaction is completed before the amine capping step. In Example 1C, halfof the capping group is replaced with ethylphenylglycidate and the otherhalf is replaced with ethyl-4-hydroxybenzoate. Once again the bisphenolA and liquid epoxy are adjusted to leave the same equivalents ofunreacted epoxy after the polymer upgrade reaction is completed. Inexample 1D, the capping group is replaced with ethyl 4-hydroxybenzoate.

The reaction products are emulsified in water as Emulsions 1A to 1 D.Additionally, a pigment-containing composition, also known as a pigmentpaste, is used. In these examples, the metal catalyst is incorporatedinto the pigment paste and the pigment paste containing the metalcatalyst is incorporated into the emulsion to establish an electrocoatbath where the metal catalyst complexes with the hydroxy-functionalfilm-forming material.

EMULSION EXAMPLE 1A

The following materials are combined in a 5 L flask with an associatedheating mantle:

diglycidyl ether of bisphenol A (DGEBA), (652.05 g, 6.4 eq. epoxy),

bisphenol A (BPA), (148.27 g, 2.0 eq. OH),

phenol,

ethyl phenylglycidate (34.14 g, 0.3 eq), and

butoxypropanol (25.16 g)

While stirring, the temperature is raised to 125° C. Subsequently,triphenyl phosphine (1.16 g) is added and the exotherm is recorded (189°C.). The mixture is then allowed to cool to 132° C., and a weight perepoxide (WPE) determination (target=525+/−25) is conducted and is 550.After cooling to 82° C. and turning off the heating mantle, 92.24 g ofSynfac 8009 (a plasticizer) is added, 1.10 eq. N of a mixture ofsecondary amines is introduced and the exotherm is recorded (105° C.).The mixture is allowed to stir for an additional 30 minutes afterreaching exotherm. After stirring for 30 minutes,3-dimethylaminopropylamine is added at 105° C. (30.46 g, 0.55 eq.), andthe exotherm is recorded (142° C.). The mixture is stirred for anadditional hour. The crosslinker (491.40 g) is added. The crosslinker isa blocked isocyanate based on polymeric MDI and monofunctional alcohols.

After achieving a homogeneous mixture, the resin and crosslinker blendis added to an acid/water mixture, under constant stirring, of deionizedwater (1152 g) and formic acid (88%) (15.57 g). After thoroughly mixingall components using a metal spatula, the solids are further reduced byaddition of water (1142 g). A flow-additive package (94 g) is added tothe acid mixture. All raw materials, including the various solvents usedabove, are industrial grade and no further purifications are made.

EMULSION EXAMPLE 1B

The following materials are combined in a 5 L flask with an associatedheating mantle:

diglycidyl ether of bisphenol A, DGEBA, (619.45 g, 6.4 eq. epoxy),

bisphenol A, BPA, (258.24 g, 2.2 eq. OH),

ethyl phenylglycidate (108.12 g, 1.0 eq), and

butoxypropanol (23.90 g)

While stirring, the temperature is raised to 125° C. Subsequently,triphenyl phosphine (1.16 g) is added and the exotherm is recorded (189°C.). The mixture is then allowed to cool to 132° C., and a WPEdetermination (target=620+/−25) is conducted and is 605. After coolingto 82° C. and turning off the heating mantle, 87.63 g of Synfac 8009 (aplasticizer) is added, 1.10 eq. N of a mixture of secondary amines isintroduced and the exotherm is recorded (105° C.). The mixture isallowed to stir for an additional 30 minutes after reaching exotherm.After stirring for 30 minutes, 3-dimethylaminopropylamine is added at107° C. (28.93 g, 0.55 eq.), and the exotherm is recorded (145° C.). Themixture is stirred for an additional hour. The crosslinker (466.83 g) isadded. The crosslinker is a blocked isocyanate based on polymeric MDIand monofunctional alcohols, such as diethylene glycol butyl ether.After achieving a homogeneous mixture, the resin and crosslinker blendis added to an acid/water mixture, under constant stirring, of deionizedwater (1152 g) and formic acid (88%) (28.93 g). After thoroughly mixingall components using a metal spatula, the solids are further reduced byaddition of water (1085 g). A flow-additive package (89.3 g) is added tothe acid mixture. All raw materials, including the various solvents usedabove, are industrial grade and no further purifications are made.

EMULSION EXAMPLE 1C

The following materials are combined in a 5 L flask with an associatedheating mantle:

diglycidyl ether of bisphenol A, DGEBA, (619.45 g, 6.4 eq. epoxy),

bisphenol A, BPA, (258.24 g, 2.2 eq. OH),

ethyl phenylglycidate (54.06 g, 0.5 eq),

ethyl 4-hydroxybenzoate (42.73 g, 0.5 eq.) and

butoxypropanol (23.90 g)

While stirring, the temperature is raised to 125° C. Subsequently,triphenyl phosphine (1.16 g) is added and the exotherm is recorded (183°C.). The mixture is then allowed to cool to 132° C., and a WPEdetermination (target=600+/−25) is conducted and is 605. After coolingto 82° C. and turning off the heating mantle, 87.63 g of Synfac 8009 (aplasticizer) is added, 1.10 eq. N of a mixture of secondary amines isintroduced and the exotherm is recorded (105° C.). The mixture isallowed to stir for an additional 30 minutes after reaching exotherm.After stirring for 30 minutes, 3-dimethylaminopropylamine is added at107° C. (28.93 g, 0.55 eq.), and the exotherm is recorded (145° C.). Themixture is stirred for an additional hour. The crosslinker (466.83 g) isadded. The crosslinker is a blocked isocyanate based on polymeric MDIand monofunctional alcohols, such as diethylene glycol butyl ether.After achieving a homogeneous mixture, the resin and crosslinker blendis added to an acid/water mixture, under constant stirring, of deionizedwater (1152 g) and formic acid (88%) (28.93 g). After thoroughly mixingall components using a metal spatula, the solids are further reduced byaddition of water (1085 g). A flow-additive package (89.3 g) is added tothe acid mixture. All raw materials, including the various solvents usedabove, are industrial grade and no further purifications are made.

EMULSION EXAMPLE 1D

The following materials are combined in a 5 L flask with an associatedheating mantle:

diglycidyl ether of bisphenol A, DGEBA, (619.45 g, 6.4 eq. epoxy),

bisphenol A, BPA, (140.86 g, 1.2 eq. OH),

ethyl 4-hydroxybenzoate (85.46 g, 0.5 eq.) and

butoxypropanol (23.90 g)

While stirring, the temperature is raised to 125° C. Subsequently,triphenyl phosphine (1.10 g) is added and the exotherm is recorded (185°C.). The mixture is then allowed to cool to 132° C., and a WPEdetermination (target=560+/−25) is conducted and is 550. After coolingto 82° C. and turning off the heating mantle, 87.63 g of Synfac 8009 (aplasticizer) is added, 1.10 eq. N of a mixture of secondary amines isintroduced and the exotherm is recorded (107° C.). The mixture isallowed to stir for an additional 30 minutes after reaching exotherm.After stirring for 30 minutes, 3-dimethylaminopropylamine is added at107° C. (28.93 g, 0.55 eq.), and the exotherm is recorded (145° C.). Themixture is stirred for an additional hour. The crosslinker (466.83 g) isadded. The crosslinker is a blocked isocyanate based on polymeric MDIand monofunctional alcohols, such as diethylene glycol butyl ether.After achieving a homogeneous mixture, the resin and crosslinker blendis added to an acid/water mixture, under constant stirring, of deionizedwater (1152 g) and formic acid (88%) (28.93 g). After thoroughly mixingall components using a metal spatula, the solids are further reduced byaddition of water (1085 g). A flow-additive package (89.3 g) is added tothe acid mixture. All raw materials, including the various solvents usedabove, are industrial grade and no further purifications are made.

The paste used in the electrodeposition formulation examples 1A-1D wasprepared as described in U.S. Pat. No. 6,951,602 to Reuter et al., whichis incorporated herein by reference.

Preparation of the Pigment Paste

Preparation of a Grinding Resin Solution having Tertiary AmmoniumGroups: In accordance with EP 0 505 445 B1, Example 1.3, anaqueous-organic grinding resin solution is prepared by reacting, in thefirst stage, 2598 parts of bisphenol A diglycidyl ether (epoxyequivalent weight (EEW) 188 g/eq), 787 parts of bisphenol A, 603 partsof dodecylphenol and 206 parts of butyl glycol in a stainless steelreaction vessel in the presence of 4 parts of triphenylphosphine at 130°C. until an EEW of 865 g/eq is reached. In the course of cooling, thebatch is diluted with 849 parts of butyl glycol and 1534 parts ofD.E.R.® 732 (polypropylene glycol diglycidyl ether, DOW Chemical, USA)and is reacted further at 90° C. with 266 parts of2,2′aminoethoxyethanol and 212 parts of N,N-dimethylaminopropylamine.After 2 hours, the viscosity of the resin solution is constant (5.3dPa·s; 40% in Solvenon® PM (methoxypropanol, BASF/Germany); cone andplate viscometer at 23° C.). It is diluted with 1512 parts of butylglycol and the base groups are partly neutralized with 201 parts ofglacial acetic acid, and the product is diluted further with 1228 partsof deionized water and discharged. This gives a 60% strengthaqueous-organic resin solution whose 10% dilution has a pH of 6.0. Theresin solution is used in direct form for paste preparation.

Preparation of the Pigment Paste: For this purpose, a premix is firstformed from 1897 parts of water and 1750 parts of the grinding resinsolution described above. Then 21 parts of Disperbyk® 110 (Byk-ChemieGmbH/Germany), 14 parts of Lanco Wax® PE W 1555 (Langer & Co./Germany),42 parts of carbon black, 420 parts of aluminum hydrosilicate ASP 200(Langer & Co./Germany), 2667 parts of titanium dioxide TI-PURE® R 900(DuPont, USA) and 189 parts of di-n-butyltin oxide are added. Themixture is predispersed for 30 minutes under a high-speed dissolverstirrer. The mixture is subsequently dispersed in a small laboratorymill (Motor Mini Mill, Eiger Engineering Ltd, Great Britain) for from 1to 15 h to a Hegmann fineness of less than or equal to 12 μm andadjusted to solids content with additional water. A separation-stablepigment paste P1 is obtained. Solids content: 60.0% (½ h at 180° C.)

Electrodeposition Formulation for Example 1A

TABLE 1 Example 1A Variables Bath Size (grams) 2500 Bath % NV 19 BathP/B 0.16 Paste P/B 3.1 Paste % NV 67.5 Emulsion % NV 44.1 Grams of PasteGrams of Emulsion Grams of Water 128 880 1491

In a 1-gallon bucket the emulsion and water are mixed with constantstirring. The paste is added while stirring.

Electrodeposition Formulation for Example 1B

TABLE 2 Example 1B Variables Bath Size (grams) 2500 Bath % NV 19 BathP/B 0.16 Paste P/B 3.1 Paste % NV 67.5 Emulsion % NV 27.1 Grams of PasteGrams of Emulsion Grams of Water 128 1433 938

In a 1-gallon bucket the emulsion and water are mixed with constantstirring. The paste is added while stirring.

Electrodeposition Formulation for Example 1C

TABLE 3 Example 1C Variables Bath Size (grams) 2500 Bath % NV 19 BathP/B 0.16 Paste P/B 3.1 Paste % NV 67.5 Emulsion % NV 32.8 Grams of PasteGrams of Emulsion Grams of Water 128 1183 1187

In a 1-gallon bucket the emulsion and water are mixed with constantstirring. The paste is added while stirring.

Electrodeposition Formulation for Example 1D

TABLE 4 Example 1D Variables Bath Size (grams) 2500 Bath % NV 19 BathP/B 0.16 Paste P/B 3.1 Paste % NV 67.5 Emulsion % NV 39.4 Grams of PasteGrams of Emulsion Grams of Water 128 985 1385

In a 1-gallon bucket the emulsion and water are mixed with constantstirring. The paste is added while stirring.

With the aqueous coating compositions of Examples 1A-1D formed, testpanels are prepared (described in detail below) to ascertain propertiesof coatings prepared from Examples 1A-1D. Tests include a MEK Double RubSolvent Resistance Test and Corrosion Test; details of these tests arefurther described below. Two types of panel substrates are employed:phosphate treated cold rolled steel (CRS) panels and bare CRS. Allpanels are 4″×6″ in dimension and are purchased from ACT The panels areelectrocoated to film builds of approximately 0.40 mil and 0.80 mil,depending on the particular test.

Voltage ladders are prepared to observe how voltage affects film buildand are tabulated for the two different substrates at three differentbake temperatures.

TABLE 5 Example 1A, phosphate treated CRS panels @ 300° F. Bake @ 325°F. Bake @ 350° F. Bake Bath Energy Film Bath Energy Film Bath EnergyFilm Voltage Temp. Consume Build Temp. Consume Build Temp. Consume Build(volts) ° F. (couls) (mils) ° F. (couls) (mils) ° F. (couls) (mils) 10090.4 34 0.499 90.0 34 0.470 89.8 34 0.438 125 89.6 34 0.517 89.6 380.480 90.2 34 0.482 150 90.4 35 0.679 90.8 35 0.668 90.8 35 0.660 17590.8 36 0.713 91 36 0.695 91.6 35 0.720 200 90.8 39 0.781 90.8 38 0.75590.6 39 0.736 225 90.6 40 0.846 90.2 40 0.797 90.6 40 0.798 250 90.6 430.942 91 44 0.943 90.8 43 0.884

TABLE 6 Example 1A, Bare CRS panels @ 300° F. Bake @ 325° F. Bake @ 350°F. Bake Bath Energy Film Bath Energy Film Bath Energy Film Voltage Temp.Consume Build Temp. Consume Build Temp. Consume Build (volts) ° F.(couls) (mils) ° F. (couls) (mils) ° F. (couls) (mils) 100 89.8 46 0.79290.0 46 0.766 90.4 47 0.766 125 89.6 48 0.955 90.0 49 0.963 90.2 490.963 150 91.2 45 1.018 92.0 45 0.957 92.4 44 0.922 175 91.8 47 1.07893.0 47 1.002 92.8 47 0.978 200 90.4 47 1.009 90.8 48 1.001 90.6 480.986 225 90.2 47 1.025 90.8 48 1.008 90.6 48 0.948 250 91.0 51 1.13591.4 50 1.073 90.8 50 1.047

TABLE 7 Example 1B, phosphate treated CRS panels @ 300° F. Bake @ 325°F. Bake @ 350° F. Bake Bath Energy Film Bath Energy Film Bath EnergyFilm Voltage Temp. Consume Build Temp. Consume Build Temp. Consume Build(volts) ° F. (couls) (mils) ° F. (couls) (mils) ° F. (couls) (mils) 10090.0 39 0.157 90.0 39 0.167 90.0 39 0.131 125 89.8 41 0.179 89.6 400.189 89.6 40 0.151 150 89.6 41 0.235 89.6 42 0.235 89.8 42 0.229 17590.4 44 0.288 89.8 44 0.302 90.0 44 0.288 200 89 49 0.461 89.6 43 0.32190.0 44 0.287 225 90.4 46 0.398 90.2 46 0.374 90.8 46 0.379 250 90.1 480.453 90.4 48 0.448 90.6 48 0.393

TABLE 8 Example 1B, Bare CRS panels @ 300° F. Bake @ 325° F. Bake @ 350°F. Bake Bath Energy Film Bath Energy Film Bath Energy Film Voltage Temp.Consume Build Temp. Consume Build Temp. Consume Build (volts) ° F.(couls) (mils) ° F. (couls) (mils) ° F. (couls) (mils) 100 90.2 — 0.28390.4 — 0.277 90.6 — 0.261 125 89.6 50 0.303 89.4 51 0.299 89.6 51 0.244150 90.2 53 0.342 90.6 53 0.312 90.8 52 0.311 175 — — 0.407 — — 0.381 —— 0.355 200 90.4 54 0.454 91.0 54 0.422 90.2 54 0.381 225 90.2 55 0.47490.8 55 0.431 90.8 55 0.468 250 90.6 62 0.538 91.0 56 0.501 91.2 570.501

TABLE 9 Example 1C, phosphate treated CRS panels @ 300° F. Bake @ 325°F. Bake @ 350° F. Bake Bath Energy Film Bath Energy Film Bath EnergyFilm Voltage Temp. Consume Build Temp. Consume Build Temp. Consume Build(volts) ° F. (couls) (mils) ° F. (couls) (mils) ° F. (couls) (mils) 10090.6 44 0.179 90.4 46 0.157 90.4 45 0.125 125 89.8 46 0.148 89.6 450.136 89.6 44 0.116 150 90.2 44 0.171 90.4 44 0.157 90.2 45 0.171 17590.2 45 0.228 90.4 45 0.222 90.0 45 0.189 200 90.2 46 0.238 90.0 460.267 90.4 46 0.252 225 90.8 52 0.399 90.4 50 0.337 90.0 51 0.361 25089.8 63 0.742 91.0 63 0.405 92.6 57 0.459

TABLE 10 Example 1C, Bare CRS panels @ 300° F. Bake @ 325° F. Bake @350° F. Bake Bath Energy Film Bath Energy Film Bath Energy Film VoltageTemp. Consume Build Temp. Consume Build Temp. Consume Build (volts) ° F.(couls) (mils) ° F. (couls) (mils) ° F. (couls) (mils) 100 90.0 51 0.20190.0 51 0.174 90.0 51 0.156 125 89.6 53 0.239 90.0 53 0.279 90.0 550.181 150 90.4 57 0.345 90.4 57 0.331 90.6 56 0.312 175 89.8 56 0.37990.4 56 0.363 90.8 58 0.351 200 90.4 60 0.455 90.4 60 0.401 90.4 600.387 225 90.4 62 0.487 89.6 68 0.690 90.4 68 0.483 250 90.6 71 0.75791.8 70 0.757 94.0 68 0.680

TABLE 11 Example 1D, phosphate treated CRS panels @ 300° F. Bake @ 325°F. Bake @ 350° F. Bake Bath Energy Film Bath Energy Film Bath EnergyFilm Voltage Temp. Consume Build Temp. Consume Build Temp. Consume Build(volts) ° F. (couls) (mils) ° F. (couls) (mils) ° F. (couls) (mils) 10089.5 34 0.230 89.5 34 0.201 89.5 34 0.210 125 90.0 38 0.275 90.1 380.249 90.3 38 0.270 150 90.3 — 0.313 90.3 — 0.301 90.2 40 0.321 175 90.141 0.370 90.3 — 0.298 90.1 43 0.361 200 89.7 43 0.405 90.0 43 0.382 90.244 0.423 225 90.1 44 0.462 90.5 44 0.445 90.3 — 0.427 250 89.0 44 0.80690.0 44 0.463 90.3 44 0.506 300 90.5 50 0.675 90.7 50 0.624 90.3 510.638

TABLE 12 Example 1D, Bare CRS panels @ 300° F. Bake @ 325° F. Bake @350° F. Bake Bath Energy Film Bath Energy Film Bath Energy Film VoltageTemp. Consume Build Temp. Consume Build Temp. Consume Build (volts) ° F.(couls) (mils) ° F. (couls) (mils) ° F. (couls) (mils) 100 89.7 39 0.33689.8 41 0.297 89.9 40 0.302 125 90.4 42 0.403 90.3 41 0.391 90.2 410.380 150 90.1 43 0.497 90.2 44 0.455 90.1 43 0.450 175 90.3 45 0.50490.1 45 0.510 90.3 49 0.502 200 90.3 49 0.511 90.4 47 0.461 90.5 470.482 225 90.0 49 0.539 90.3 49 0.519 89.9 50 0.573 250 90.4 54 0.57790.4 54 0.549 90.7 50 0.635 300 90.3 57 0.716 89.7 56 0.669 90.7 580.713

MEK Double Rub Solvent Resistance Test:

As an initial screening tool to assess cure, methyl ethyl ketone (MEK)double rubs are carried out. The panels are CRS with and without thezinc phosphate treatment and the coating compositions are applied andcured at various times and temperatures to form cured coatings.

Using a piece of cheese cloth soaked with MEK and wrapped around theindex finger, a total of 25, and 50, double rubs are carried out usingslight pressure. After the double rubs, the panels are rated: 0 (nochange), 1 (slight change), 3 (moderate change), and 5 (severechange—metal exposure, failure).

Complete data for the MEK double rub solvent resistance test of Examples1A-1D are found in Tables 13-20. Data for a comparative commercialcoating composition, CathoGuard® 500 (BASF Corp.), is presented in Table21. In addition to MEK data, the tables also include gloss data measuredat a 60° angle.

TABLE 13 Example 1A, phosphate treated CRS panels @ 300° F. Bake @ 325°F. Bake @ 350° F. Bake Voltage MEK 25 MEK 50 MEK 25 MEK 50 MEK 25 MEK 50(volts) rubs rubs Gloss rubs rubs Gloss rubs rubs Gloss 100 5 5 100.0 12 97.2 0 1 94.6 125 5 5 98.3 1 2 91.5 0 0 100.8 150 3 3 99.6 1 1 99.9 00 91.3 175 3 3 98.8 1 1 101.7 0 0 98.7 200 3 3 100.3 1 1 101.1 0 1 96.6225 3 3 99.8 1 1 99.5 0 1 91.5 250 3 3 98.1 1 2 93.5 0 1 83.5

TABLE 14 Example 1A, Bare CRS panels @ 300° F. Bake @ 325° F. Bake @350° F. Bake Voltage MEK 25 MEK 50 MEK 25 MEK 50 MEK 25 MEK 50 (volts)rubs rubs Gloss rubs rubs Gloss rubs rubs Gloss 100 2 3 98.7 1 1 99.9 01 97.9 125 2 3 97.0 1 1 99.8 0 0 95.2 150 2 3 96.2 1 1 100.5 0 0 95.6175 2 3 99.7 1 1 98.4 0 0 95.4 200 2 3 101.1 1 1 97.2 0 0 95.2 225 2 398.6 1 1 95.0 0 0 88.5 250 2 3 97.8 1 1 92.6 — — —

TABLE 15 Example 1B, phosphate treated CRS panels @ 300° F. Bake @ 325°F. Bake @ 350° F. Bake Voltage MEK 25 MEK 50 MEK 25 MEK 50 MEK 25 MEK 50(volts) rubs rubs Gloss rubs rubs Gloss rubs rubs Gloss 100 5 5 99.6 5 594.0 1 1 78.3 125 5 5 97.5 4 4 92.0 0 1 79.7 150 5 5 96.5 4 5 91.5 0 180.6 175 5 5 97.1 3 4 91.5 0 1 86.1 200 5 5 98.6 4 5 937 0 1 87.2 225 55 100.0 3 3 99.1 1 1 87.4 250 5 5 99.5 2 2 99.8 0 1 96.7 300 2 3 90.0 —— — — — —

TABLE 16 Example 1B, Bare CRS panels @ 300° F. Bake @ 325° F. Bake @350° F. Bake Voltage MEK 25 MEK 50 MEK 25 MEK 50 MEK 25 MEK 50 (volts)rubs rubs Gloss rubs rubs Gloss rubs rubs Gloss 100 5 5 98.6 2 3 94.7 12 90.7 125 5 5 98.5 2 3 94.0 1 1 87.3 150 5 5 98.6 2 3 93.0 1 1 87.1 1755 5 99.4 2 2 96.2 0 1 88.1 200 5 5 100.0 1 2 96.5 — — — 225 4 5 99.4 1 293.8 0 0 93.0 250 4 4 94.9 1 2 97.7 0 0 90.2

TABLE 17 Example 1C, phosphate treated CRS panels @ 300° F. Bake @ 325°F. Bake @ 350° F. Bake Voltage MEK 25 MEK 50 MEK 25 MEK 50 MEK 25 MEK 50(volts) rubs rubs Gloss rubs rubs Gloss rubs rubs Gloss 100 5 5 98.4 4 585.1 4 5 81.5 125 5 5 88.6 5 5 86.8 2 3 79.2 150 — — — 4 5 91.4 2 3 82.0175 5 5 97.9 4 4 90.8 1 2 75.4 200 5 5 99.2 3 4 90.7 0 0 74.4 225 4 599.4 2 2 85.5 0 0 74.5 250 4 4 98.5 2 2 96.3 0 0 76.7

TABLE 18 Example 1C, Bare CRS panels @ 300° F. Bake @ 325° F. Bake @350° F. Bake Voltage MEK 25 MEK 50 MEK 25 MEK 50 MEK 25 MEK 50 (volts)rubs rubs Gloss rubs rubs Gloss rubs rubs Gloss 100 5 5 96.7 2 3 84.0 23 79.9 125 5 5 99.9 2 3 79.8 0 1 80.5 150 5 5 98.6 2 3 96.4 0 1 89.3 1755 5 100 2 3 96.1 0 0 85.0 200 5 5 95.7 0 1 92.3 0 0 81.5 225 5 5 95.0 01 94.0 0 0 96.6 250 5 5 98.8 1 1 95.0 0 0 87.0

TABLE 19 Example 1D, phosphate treated CRS panels @ 300° F. Bake @ 325°F. Bake @ 350° F. Bake Voltage MEK 25 MEK 50 MEK 25 MEK 50 MEK 25 MEK 50(volts) rubs rubs Gloss rubs rubs Gloss rubs rubs Gloss 100 4 5 80.8 1 284.3 0 1 70.5 125 4 4 91.0 0 1 80.4 0 0 66.3 150 4 4 86.1 0 0 72.3 0 065.8 175 3 4 89.2 0 1 73 0 0 69.2 200 3 4 94.2 1 2 82.7 0 0 69.7 225 2 397.4 0 0 93.5 0 0 81.7 250 2 2 92.9 0 0 52.4 — — — 300 — — — 0 0 76.1 00 71.4

TABLE 20 Example 1D, Bare CRS panels @ 300° F. Bake @ 325° F. Bake @350° F. Bake Voltage MEK 25 MEK 50 MEK 25 MEK 50 MEK 25 MEK 50 (volts)rubs rubs Gloss rubs rubs Gloss rubs rubs Gloss 100 4 4 95.9 1 2 86.2 00 81.4 125 4 4 99.4 0 1 85.9 0 0 77.5 150 4 4 87.8 0 1 86.9 0 0 77.7 1751 2 92.5 0 1 85.8 0 0 82.7 200 1 2 95.7 0 1 85.8 0 0 81.8 225 1 2 95.3 01 82.5 0 0 71.2 250 1 2 94.8 0 0 83.8 0 0 85.5 300 1 2 93.7 0 0 96.3 0 074.8

TABLE 21 Control Cathogard 500, phosphate treated CRS panels @ 300° F.Bake @ 325° F. Bake @ 350° F. Bake Voltage MEK 25 MEK 50 MEK 25 MEK 50MEK 25 MEK 50 (volts) rubs rubs Gloss rubs rubs Gloss rubs rubs Gloss150 5 5 92.3 4 5 98.0 0 1 83.4

Corrosion Test (Double Scab):

Bare CRS panels were coated with the urethane coating compositions ofExamples 1A-1D to form urethane coatings of approximately 0.4 mil; threepanels were coated for each example and at each temperature. Thesepanels were cured at approximately 300° F., 325° F., and 350° F. forapproximately 20 minutes.

After coating, each panel was scribed with a scab having the appearanceof an “X.” Initial adhesion and shot blast is omitted in the CorrosionTest. The daily test sequence and test cycle were carried out by placingthe panels in test on any weekday between Tuesday through Friday. Atotal of 25 test cycles were carried out, with each cycle equaling oneday. The cycle was first started by subjecting each panel to a 60 minutebake with an oven temperature of 60° C., followed by gradual cooling toroom temperature for 30 minutes. The salt immersion and humidity portionof the test was done by first placing each panel in an aqueous solutionof 5% (wt.) NaCl for 15 minutes followed by drying at ambienttemperature for 75 minutes. This was performed once a week. Afterimmersion, the panels were placed in a humidity cabinet (85% humidity)set at 60° C. for 22.5 hr. On weekends, the panels were allowed toremain in the humidity cabinet. After the 36 day, 25 cycles, the panelswere removed from testing, thoroughly rinsed and scraped with a metalspatula to remove any loose paint. The average corrosion diameter wasthen obtained by using a caliper and taking random measurements alongeach side of the scab, this was done in three different panels all underthe same conditions.

The results of the Corrosion Test are summarized in FIG. 1.

EXAMPLE 2 Electrodepositable Acrylic Coating Composition IncludingNonionic Metal Coordinating Structures

Production of a Cationized Resin (Component A): (1) A flask equippedwith a stirrer, thermometer, nitrogen inlet and reflux condenser ischarged with 541 parts of butyl cellosolve and heated to 120° C. withstirring. While the temperature is maintained, a mixture of thefollowing compounds is added dropwise over a period of 3 hours: styrene(484 parts); 2-allyloxytetrahydropyran (26 parts); 2-hydroxyethylmethacrylate (340 parts); n-butyl acrylate (114 parts); “FM-3” (113parts) (FM-3 is a product of Daicel Chemical Industries, ahydroxyl-containing polymerizable unsaturated compound prepared byaddition of ε-caprolactone to 2-hydroxyethyl methacrylate); acrylic acid(57 parts); and azoisobutyronitrile (68 parts).

After completion of the dropwise addition, the resulting mixture ismaintained at the same temperature for 1 hour. A mixed solution of 11.3parts of azoisobutyronitrile and 85 parts of butyl cellosolve is addeddropwise over a period of 1 hour. The mixture is maintained at the sametemperature for 1 hour, thus giving a carboxyl- and hydroxyl-containingacrylic polymer solution having a solids content of 63%. The polymer hasan acid value of about 40 mg KOH/g, a hydroxyl value of about 140 mgKOH/g, and a number average molecular weight of about 13,000

(2) Into a flask equipped with a stirrer, thermometer, nitrogen inletand reflux condenser, 1,000 parts of 4,4′-diphenylmethane diisocyanateis placed and dissolved at 50° C. At the same temperature, 750 parts ofdiethylene glycol monoethyl ether is added and the reaction is allowedto proceed until the isocyanate content of the solids becomes 5.76%,thus giving a partially blocked isocyante compound.

(3) A flask equipped with a stirrer, thermometer, nitrogen inlet andreflux condenser is charged with 272 parts of bisphenol A, 815 parts ofa bisphenol A diglycidyl ether-type epoxy resin having an epoxyequivalent of 185, and 0.25 parts of tetraethylammonium bromide. Thereaction is allowed to proceed at 150° C. until the epoxy equivalent ofthe reaction product becomes 570. After the reaction mixture is cooledto 120° C., 440 parts of the partially blocked isocyanate compoundobtained in (2) is added and the reaction is allowed to proceed at 110°C. for 2 hours. Subsequently, 200 parts of butyl cellosolve, 650 partsof the above acrylic polymer solution having a solids content of 63% and160 parts of diethanolamine are added. The reaction is allowed toproceed at 110° C. until no epoxy groups remain. The mixture is dilutedwith 375 parts of butyl cellosolve, giving a hydroxyl- andamino-containing acrylic resin solution having a solids content of 72%.The resin before introduction of cationic groups has an epoxy equivalentof about 700, a hydroxyl value of about 80 mg KOH/g, and a numberaverage molecular weight of about 2,500.

Production of an Acrylic Resin (Component B): Butyl cellosolve®(n-butoxyethanol) (184 parts) is heated to 130° C. and a mixture of thefollowing compounds is added dropwise over a period of 3 hours: styrene(296 parts); 2-allyloxytetrahydropyran (16 parts); 2-hydroxyethylmethacrylate (216 parts); “FM-3” (192 parts); dimethylaminoethylmethacrylate (80 parts); and azoisobutyronitrile (40 parts).

The reaction mixture is aged at the same temperature for 1 hour, andthen a mixed solution of 8 parts of azobisdimethylvaleronitrile and 56parts of methyl isobutyl ketone is added dropwise at the sametemperature over a period of 1 hour. The reaction mixture is furtheraged at the same temperature for 1 hour and diluted with butylcellosolve®, to produce a hydroxyl- and amino-containing acrylic resinsolution with a solids content of 70%. The resin obtained has a numberaverage molecular weight of about 15,000, a hydroxyl value of about 145mg KOH/g and an amine value of about 36 mg KOH/g.

Production of an Isocyanate Crosslinking Agent (Component C): 268 partsof diethylene glycol monoethyl ether is added dropwise to 250 parts of4,4′diphenylmethane diisocyanate at 50° C., then the reaction is allowedto proceed at 80° C. until no free isocyanate groups remain. Acompletely blocked polyisocyante compound is thereby obtained.

A cationic electrodeposition coating composition is prepared by mixing:cationized resin (Component A) (88 parts); acrylic resin (Component B)(12 parts); and isocyanate crosslinking agent (Component C) (7 parts).The mixture is neutralized with 0.3 equivalent of acetic acid anddiluted with water to provide a cationic electrodeposition coatingcomposition having a solids content of 20%.

The cationic electrodeposition coating composition is coated on zincphosphate cold rolled steel panels at a bath temperature of 28° C. toform electrodeposition coating films having a thickness of about 20-25μm when cured. The coating films are cured by heating at 1600 for 10minutes.

The description of the technology is merely exemplary in nature and,thus, variations that do not depart from the gist of the presentdisclosure are intended to be within the scope of the invention. Suchvariations are not to be regarded as a departure from the spirit andscope of the invention.

1. A film-forming material comprising: a resin, wherein the resinincludes at least one pendent group comprising a nonionic metalcoordinating structure and at least one group reactive with acrosslinker.
 2. A film-forming material of claim 1, wherein the resin isan epoxy, acrylic, polyurethane, polycarbonate, polysiloxane,aminoplast, or polyester resin.
 3. A film-forming material of claim 1,wherein the at least one group reactive with a crosslinker is anepoxide, hydroxyl, carboxyl, carbamate, or amine group.
 4. Afilm-forming material of claim 1, wherein the resin comprises theformula:

wherein, X¹ and X² are independently hydrogen, hydroxyl, epoxide, oramine functional monovalent radicals; each R¹ and R² is independentlyalkylene or arylene divalent radicals; R³ is an alkylene or arylenedivalent radical comprising a nonionic metal coordinating structure; nis a number from 1 to about 12; m is a number from 0 to about 12; and pis a number from 1 to about
 12. 5. A film-forming material of claim 4,wherein R¹ and R² are 2,2-diphenylpropane divalent radicals.
 6. Afilm-forming material of claim 1, wherein the nonionic metalcoordinating structure comprises a first electron-rich functional group.7. A film-forming material of claim 6, wherein the first electron-richfunctional group includes an atom selected from a group consisting of:nitrogen, oxygen, phosphorous, sulfur, silicon, and carbon.
 8. Afilm-forming material of claim 6, wherein the first electron-richfunctional group is a member of the group consisting of an ester, aketone, an ether, and a hydroxyl.
 9. A film-forming material of claim 6,wherein the nonionic metal coordinating structure further comprises asecond electron-rich functional group, wherein the second electron richfunctional group is in an alpha- or beta-position relative to the firstelectron-rich functional group.
 10. A film-forming material of claim 1,further comprising a metal or metal compound coordinated by the nonionicmetal coordinating structure.
 11. A film-forming material of claim 10,wherein the metal or metal compound is selected from a group consistingof M, MO, M₂O₃, M(OH)_(n), R_(x)MO, and combinations thereof; wherein, Mis a metal selected from the group consisting of Al, Bi, Ce, Cu, Fe, Pb,Sn, Sb, Ti, Y, Zn, and Zr; n is an integer satisfying the valency of M;R is an alkyl or aromatic group; and x is an integer from 1 to
 6. 12. Afilm-forming material of claim 10, wherein the metal or metal compoundcomprises a metal catalyst selected from a group consisting ofdibutyltin oxide, dibutyltin dilaurate, zinc oxide, bismuth oxide, tinoxide, yttrium oxide, copper oxide, and combinations thereof.
 13. Acurable film-forming material comprising a product of a reaction of aresin, wherein the resin has at least one group reactive with anucleophile, and a nucleophilic ligand, wherein the nucleophilic ligandhas the formula:X³—R⁴—X⁴ wherein, X³ is a hydroxyl or carboxyl monovalent radical; R⁴ isan alkylene or arylene divalent radical having a molecular weight fromabout 90 g/mol to about 5000 g/mol and a nonionic metal coordinatingstructure; and X⁴ is a hydrogen, hydroxyl, or carboxyl monovalentradical.
 14. A film-forming material of claim 13, wherein the resin isan epoxy, acrylic, polyurethane, polycarbonate, polysiloxane,aminoplast, or polyester resin.
 15. A film-forming material of claim 13,wherein the at least one group reactive with a nucleophile is an epoxidegroup.
 16. A film-forming material of claim 13, wherein the nonionicmetal coordinating structure comprises a first electron-rich functionalgroup.
 17. A film-forming material of claim 16, wherein the firstelectron-rich functional group includes an atom selected from a groupconsisting of: nitrogen, oxygen, phosphorous, sulfur, silicon, andcarbon.
 18. A film-forming material of claim 16, wherein the firstelectron-rich functional group is a member of the group consisting of anester, a ketone, an ether, and a hydroxyl.
 19. A film-forming materialof claim 16, wherein the nonionic metal coordinating structure furthercomprises a second electron-rich functional group, wherein the secondelectron rich functional group is in an alpha- or beta-position relativeto the first electron-rich functional group.
 20. A film-forming materialof claim 13, wherein the nucleophilic ligand is selected from a groupconsisting of ethyl-2-hydroxybenzoate, ethyl-4-hydroxybenzoate,4-hydroxy-1-(4-hydroxyphenyl)pentan-2-one,1-(2-hydroxy-6-methoxyphenyl)ethanone, and combinations thereof.
 21. Afilm-forming material of claim 13, wherein the resin is diglycidyl etherof bisphenol A.
 22. A film-forming material of claim 13, wherein thereaction further includes a member selected from a group consisting ofbisphenol A, bisphenol F, phenol, metal or metal compound, andcombinations thereof.
 23. A film-forming material of claim 22, whereinthe metal or metal compound is coordinated by the nonionic metalcoordinating structure.
 24. A film-forming material of claim 22, whereinthe metal or metal compound is selected from a group consisting of M,MO, M₂O₃, M(OH)_(n), R_(x)MO, and combinations thereof; wherein, M is ametal selected from the group consisting of Al, Bi, Ce, Cu, Fe, Pb, Sn,Sb, Ti, Y, Zn, and Zr; n is an integer satisfying the valency of M; R isan alkyl or aromatic group; and x is an integer from 1 to
 6. 25. Afilm-forming material of claim 22, wherein the metal or metal compoundcomprises a metal catalyst selected from a group consisting of dibutyltin oxide, dibutyl tin dilaurate, zinc oxide, bismuth oxide, tin oxide,yttrium oxide, copper oxide, and combinations thereof.
 26. Afilm-forming material comprising a product of a reaction of a resin,wherein the resin has at least one group reactive with an electrophile,and an electrophilic ligand, wherein the electrophilic ligand has theformula:X⁵—R⁵—X⁶ wherein, X⁵ is an epoxide or halide monovalent radical; R⁵ isan alkylene or arylene divalent radical having a molecular weight fromabout 90 g/mol to about 5000 g/mol and a nonionic metal coordinatingstructure; and X⁶ is a hydrogen, epoxide, or halide monovalent radical.27. A film-forming material of claim 26, wherein the resin is an epoxy,acrylic, polyurethane, polycarbonate, polysiloxane, aminoplast, orpolyester resin.
 28. A film-forming material of claim 26, wherein the atleast one group reactive with an electrophile is a hydroxyl group.
 29. Afilm-forming material of claim 26, wherein the nonionic metalcoordinating structure comprises a first electron-rich functional group.30. A film-forming material of claim 29, wherein the first electron-richfunctional group includes an atom selected from a group consisting of:nitrogen, oxygen, phosphorous, sulfur, silicon, and carbon.
 31. Afilm-forming material of claim 29, wherein the first electron-richfunctional group is a member of the group consisting of an ester, aketone, an ether, and a hydroxyl.
 32. A film-forming material of claim29, wherein the nonionic metal coordinating structure further comprisesa second electron-rich functional group, wherein the second electronrich functional group is in an alpha- or beta-position relative to thefirst electron-rich functional group.
 33. A film-forming material ofclaim 29, wherein the electrophilic ligand is selected from a groupconsisting of 3-methyl-1-(oxiran-2-yl)but-3-en-2-one,ethylphenylglycidate, and combinations thereof.
 34. A film-formingmaterial of claim 29, wherein the resin is bisphenol A.
 35. Afilm-forming material of claim 29, wherein the reaction further includesa member selected from a group consisting of diglycidyl ether ofbisphenol A, phenol, metal or metal compound, and combinations thereof.36. A film-forming material of claim 35, wherein the metal or metalcompound is coordinated by the nonionic metal coordinating structure.37. A film-forming material of claim 35, wherein the metal or metalcompound is selected from a group consisting of M, MO, M₂O₃, M(OH)_(n),R_(x)MO, and combinations thereof; wherein, M is a metal selected fromthe group consisting of Al, Bi, Ce, Cu, Fe, Pb, Sn, Sb, Ti, Y, Zn, andZr; n is an integer satisfying the valency of M; R is an alkyl oraromatic group; and x is an integer from 1 to
 6. 38. A film-formingmaterial of claim 35, wherein the metal or metal compound comprises ametal catalyst selected from a group consisting of dibutyl tin oxide,dibutyl tin dilaurate, zinc oxide, bismuth oxide, tin oxide, yttriumoxide, copper oxide, and combinations thereof.